Polymerizable higher diamondoid derivatives

ABSTRACT

Higher diamondoid derivatives capable of taking part in polymerization reactions are disclosed as well as intermediates to these derivatives, polymers formed from these derivatives and methods for preparing the polymers.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 10/046,486 filed Jan.16, 2002, now U.S. Pat. No. 6,858,700, which claimed priority under 35U.S.C. §119(e) to U.S. Provisional Application No. 60/262,842, filedJan. 19, 2001 and to U.S. Provisional Application No. 60/348,032, filedOct. 26, 2001, all of which are incorporated by reference.

BACKGROUND OF THE INVENTION Field of the Invention

This invention is directed to higher diamondoid derivatives containingmoieties that are capable of undergoing polymerization. This inventionis further directed to processes for polymerizing such derivatives, tochemical intermediates useful for the synthesis of such derivatives andto polymers based upon these derivatives.

References

The following publications and patents are cited in this application assuperscript numbers:

¹Fort, Jr., et al., Adamantane: Consequences of the DiamondoidStructure, Chem. Rev., 64:277-300 (1964).

²Capaldi, et al., Alkenyl Adamantanes, U.S. Pat. No. 3,457,318, issuedJul. 22, 1969.

³Thompson, Polyamide Polymer of Diamino Methyl Adamantane andDicarboxylic Acid, U.S. Pat. No. 3,832,332, issued Aug. 27, 1974.

⁴Baum, et al., Ethynyl Adamantane Derivatives and Methods ofPolymerization Thereof, U.S. Pat. No. 5,017,734, issued May 21, 1991.

⁵Ishii, et al., Polymerizable Adamantane Derivatives and Process forProducing Same, U.S. Pat. No. 6,235,851, issued May 22, 2001.

⁶McKervey, et al., Synthetic Approaches to Large DiamondoidHydrocarbons, Tetrahedron, 36:971-992 (1980).

⁷Lin, et al., Natural Occurrence of Tetramantane (C22H28), Pentamantane(C26H32) and Hexamantane (C30H36) in a Deep Petroleum Reservoir, Fuel,74(10):1512-1521 (1995).

⁸Chen, et al., Isolation of High Purity Diamondoid Fractions andComponents, U.S. Pat. No. 5,414,189, issued May 9, 1995.

⁹Balaban et al., Systematic Classification and Nomenclature of DiamondHydrocarbons-I, Tetrahedron. 34, 3599-3606 (1978).

All of the above publications and patents are herein incorporated byreference in their entirety to the same extent as if each individualpublication or patent was specifically and individually indicated to beincorporated by reference in its entirety.

State of the Art

Diamondoids are cage-shaped hydrocarbon molecules possessing rigidstructures resembling tiny fragments of a diamond crystal lattice asdescribed by Fort, Jr., et al.¹ Adamantane is the smallest member of thediamondoid series and consists of a single cage structure of the diamondcrystal lattice. Diamantane contains two adamantane subunits face-fusedto each other, triamantane three, tetramantane four, and so on. Whilethere is only one isomeric form of adamantane, diamantane andtriamantane, there are four different isomeric tetramantanes (i.e., fourdifferent shapes containing four adamantane subunits). Two of theisomeric tetramantanes are enantiomeric. The number of possible isomersincreases rapidly with each higher member of the diamondoid series.

Among other properties, diamondoids have by far the mostthermodynamically stable structures of all possible hydrocarbons thatpossess their molecular formulas due to the fact that diamondoids havethe same internal “crystalline lattice” structure as diamonds. It iswell established that diamonds exhibit extremely high tensile strength,extremely low chemical reactivity, electrical resistivity greater thanaluminum trioxide (Al₂O₃), excellent thermal conductivity, and superboptical properties.

Adamantane, which is commercially available, has been studiedextensively. The studies have been directed to a number of areas, suchas thermodynamic stability, functionalization and properties ofadamantane-containing materials. For instance, the following patentsdescribe adamantane derivatives and adamantane-based polymers. U.S. Pat.No. 3,457,318 teaches the preparation of polymers from alkenyladamantanes;² U.S. Pat. No. 3,832,332 describes a polyamide polymerformed from alkyladamantane diamine;³ U.S. Pat. No. 5,017,734 discussesthe formation of thermally stable resins from ethynyl adamantanederivatives;⁴ and, U.S. Pat. No. 6,235,851 reports the synthesis andpolymerization of a variety of adamantane derivatives.⁵

The higher diamondoids, which include the tetramantanes, pentamantanes,etc., have received comparatively little attention. In fact, prior tothe work of inventors Dahl and Carlson embodied in U.S. PatentApplication Ser. No. 60/262,842 filed Jan. 19, 2001 and numeroussubsequent filings, these compounds were nearly hypothetical with onlyone such compound having been synthesized and a few others tentativelyidentified (but not isolated). More specifically, McKervey, et al.reported the synthesis of anti-tetramantane in low yields using alaborious, multistep process.⁶ Lin, et al. have suggested the existenceof tetramantane, pentamantane and hexamantane in deep petroleumreservoirs from mass spectroscopy alone and without any attempt toisolate materials.⁷ The possible presence of tetramantane andpentamantane in pot material recovered after a distillation of adiamondoid-containing feedstock has been discussed by Chen, et al.⁸

SUMMARY OF THE INVENTION

This invention is directed to higher diamondoids that have beenderivatized to contain moieties which are capable of undergoingpolymerization reactions or being bonded to polymers, to processes forpolymerizing these derivatized higher diamondoids, to intermediatesuseful in forming these derivatives; and to polymers formed from thesederivatized higher diamondoids.

Thus, in one aspect this invention is related to polymerizable higherdiamondoid derivatives which are higher diamondoids which have one ormore polymerizable substituent groups substituting for originalhydrogens. Polymerizable higher diamondoid derivatives may berepresented by Formula I below:

wherein D is a higher diamondoid nucleus; and R¹, R², R³, R⁴, R⁵ and R⁶are independently selected from a group consisting of hydrogen and oneor more polymerizable moieties; provided there is at least onepolymerizable moiety on the compound. Preferably, the compound containseither one or two polymerizable moieties.

This invention also relates to intermediates useful in the synthesis ofsuch higher diamondoid derivatives. These higher diamondoidintermediates may be represented by Formula II below:

wherein D is as set forth in Formula I and at least one of R¹⁰—R¹⁵ is acovalently attached moiety which can be converted to a polymerizablemoiety or which, in some cases, may be a polymerizable moiety as well.The remaining R′s are hydrogens.

In the intermediates represented by Formula II, R¹⁰, R¹¹, R¹², R¹³, R¹⁴and R¹⁵ are preferably independently selected from a group of moietiesconsisting of —H, —F, —Cl, —Br, —I, —OH, —SH, —NH₂, —NHCOCH₃, —NHCHO,—CO₂H, —CO₂R′, —COCl, —CHO, —CH₂OH, ═O, —NO₂, —CH═CH₂, —C≡CH and —C₆H₅;where R′ is alkyl (preferably ethyl) provided that R¹⁰, R¹¹, R¹², R¹³,R¹⁴ and R¹⁵ are not all hydrogen. Typically one or two of R¹⁰—R¹⁵ arenonhydrogen moieties and the remaining R′s are hydrogens. Theseintermediates can be present in reaction media and the like inconcentrations of at least about 10 ppm and especially at least about100 ppm. Mixtures of these intermediates may be used as well.

In another aspect, this invention is directed to methods of obtainingpolymers which comprise higher diamondoids. These methods comprise: a)selecting one or more higher diamondoid derivatives of Formula I, aloneor in combination with other polymerizable materials; b) subjecting thematerials selected in a) to polymerization or coupling conditionsthereby forming a higher diamondoid-containing polymer; and c)recovering the higher diamondoid-containing polymer.

In yet another aspect, this invention is directed to polymers whichcontain higher diamondoids as recurring units.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A illustrates the cage-shaped structure of diamondoids and theircorrelation to diamonds. Specifically, illustrated is the correlation ofthe structures of diamondoids to subunits of the diamond crystallattice.

FIG. 1B illustrates a variety of representative derivatized higherdiamondoids carrying one or two polymerizable moieties.

FIG. 2A illustrates that higher diamondoids (in this case[1(2)3]-tetramantane) have quaternary (4°), tertiary (bridgehead, 3°)and secondary (2°) carbons.

FIG. 2B shows a carbon numbering sequence we used for the four isomerictetramantanes.

FIG. 2C shows the numbering scheme of a representative pentamantane.

FIG. 2D shows the numbering scheme of a representative hexamantane.

FIG. 2E shows the numbering scheme of a representative octamantane.

FIG. 2F shows the numbering scheme of a representative undecamantane.

FIG. 3A shows representative pathways by which higher diamondoidcarbocations are generated during the synthesis of diamondoidderivatives.

FIG. 3B shows representative pathways by which higher diamondoids arederivatized via higher diamondoid carbocations (S_(N)1 reactions).

FIG. 3C shows representative pathways by which higher diamondoids arederivatized via eletrophilic substitution reactions (S_(E)2 reactions).

FIGS. 4A-4H are eight schematic chemical formulae and equations showingthe structures and preparation of eight representative higherdiamondoid-containing polymers.

FIG. 4I is a table of representative polymerizable higher diamondoidderivatives and representative polymers they enable.

FIGS. 5A-5C illustrate exemplary polymer materials that contain higherdiamondoids as recurring units.

FIGS. 5D-5F illustrate the variety of carbon attachment sites on adecamantane molecule and how attachments to different sites in a polymermay result in cross-linked materials of varying rigidity.

FIGS. 5G and 5H illustrate with both carbon framework and CPK structuresexemplary chiral polymers prepared from enantiomeric higher diamondoidderivatives, in this case one of the enantiomeric tetramantanes.

FIG. 6 illustrates the gas chromatogram of a gas condensate feedstock;one of the original feedstocks used in the Examples (Feedstock A).

FIG. 7 gives a flow chart representing the various steps used in theisolation of higher diamondoid-containing fractions and individualhigher diamondoid components. Note that the steps can in some cases beused in a different sequence and possibly skipped as discussed in theExamples.

FIGS. 8A and 8B are compilations of the GC/MS and HPLC properties ofvarious higher diamondoids included in this application.

FIG. 9 illustrates a high temperature simulated distillation profile ofFeedstock B using the atmospheric distillation 650° F.+bottoms asfeedstock. This figure also illustrates the targeted cut points (1-10)we used for higher diamondoid isolations.

FIG. 10 is a chart illustrating distillation of cuts of a higherdiamondoid-containing feedstock (Fedstock B, atmospheric distillationresidue) showing cut selections to favor the enrichment of specificgroups of higher diamondoids.

FIGS. 11A and 11B illustrate gas chromatograms (FID) of distillatefraction #6 (Table 5B) of Feedstock B 650° F.+distillation bottoms, andthe resulting product of pyrolytic processing. These figures show thatnondiamondoid components have been destroyed by the pyrolytic processingand that higher diamondoids especially hexamantanes have beenconcentrated and made available for isolation.

FIGS. 12A and 12B are charts illustrating elution sequences for avariety of individual higher diamondoids (hexamantanes) on two differentHPLC chromatography columns: ODS and Hypercarb.

FIGS. 13A and 13B illustrate GC/MS total ion chromatogram (TIC) and massspectrum of hexamantane #13 isolated using two different HPLC columns asshown in Example 1.

FIGS. 14A and 14B illustrate the preparative capillary gaschromatographic data for hexamantane isolations carried out in Example2. FIG. 14A shows the first column cuts, containing two of thehexamantanes from Feedstock B that were sent to the secund column. FIG.14B shows the second column peaks isolated and sent to the traps. Usingthis procedure pure hexamantanes were isolated. Hexamantane #2 was thesecond hexamantane to elute in our GC/MS assay, while hexamantane #8 wasthe eighth to elute.

FIGS. 15A and 15B illustrate the GC/MS total ion chromatogram and massspectrum of hexamantane #2 in FIG. 13.

FIGS. 15C and 15D illustrate the GC/MS total ion chromatogram and massspectrum of hexamantane #8.

FIG. 16 illustrates the preparative capillary gas chromatographic datafor tetramantane isolations carried out in Example 3. The first columnshows cuts made on distillate fraction 33, Feedstock A. The bold facenumbers refer to peaks of the tetramantanes. The second column showspeaks isolated and sent to the traps. The circled numbered peaks (2, 4,and 6) are the tetramantanes. It is noted that both enantiomers of theoptically-active tetramantane are contained within one of these peaks.

FIGS. 17-34 relate to the preparation of brominated higher diamondoids(tetramantanes and alkyltetramantanes).

FIG. 17 is a total ion chromatogram of a tetramantane andalkyltetramantane-containing starting material.

FIG. 18 illustrates the GC/MS total ion chromatogram showing mono, diand tri brominated tetramantanes.

FIG. 19 shows the presence of monobrominated tetramantanes in the totalion chromatogram of the reaction product showing that these compoundsare the major components within this GC/MS retention time range.

FIG. 20 shows the presence of polybrominated tetramantanes in abrominated tetramantane product as the major components within thisGC/MS retention time range.

FIG. 21 shows the presence on a monobrominated tetramantane eluting at12.038 in the total ion chromatogram of the reaction product.

FIG. 22 is the mass spectrum of a monobrominated tetramantane with GC/MSretention time of 12.038 minutes. The based peak in this spectrum is the371 m/z molecular ion.

FIG. 23 shows the presence of monobrominated methyltetramantanes in thetotal ion chromatogram of the reaction product.

FIG. 24 is the mass spectra of monobrominated methyltetramantanes withGC/MS retention times of 11.644 and 11.992 minutes. The base peaks inthese spectra are both the 385 m/z molecular ion.

FIG. 25 shows the presence of brominated dimethyl tetramantanes in thetotal ion chromatogram of the reaction product.

FIG. 26 is the mass spectrum of the monobrominated dimethyltatramantanewith GC/MS retention time of at 12.192 minutes.

FIG. 27 shows the presence of dibrominated tetramantanes in the totalion chromatogram of the reaction product.

FIG. 28 is the mass spectrum of a dibrominated tetramantane with GC/MSretention time of 15.753 minutes. The base peak in this spectrum is the447 m/z molecular ion.

FIG. 29 shows the presence of dibrominated methyltetramantanes in thetotal ion chromatogram of the reaction product.

FIG. 30 is the mass spectrum of a dibrominated methyltetramantane withGC/MS retention time of 15.879 minutes. The base peak in this spectrumis the 461 m/z molecular ion.

FIG. 31 shows the presence of tribrominated tetramantanes in the totalion chromatogram of the reaction product.

FIG. 32 is the mass spectrum of a tribrominated tetramantane with GC/MSretention time of 17.279 minutes. The base peak in this spectrum is the527 m/z molecular ion.

FIG. 33 shows the presence of tribrominated methyltetramantanes in thetotal ion chromatogram of the reaction product.

FIG. 34 is the mass spectrum of a tribrominated methyltetramantane withGC/MS retention time of 15.250 minutes. The molecular ion is 541 m/z.

FIGS. 35-42 depict a variety of additional polymers that may be preparedin accord with this invention and representative components forincorporation into such polymers.

DETAILED DESCRIPTION OF THE INVENTION

This Detailed Description is presented in the following subsections:

Definitions

Higher Diamondoids and Their Recovery

The Higher Diamondoid Derivatives

The Higher Diamondoid Intermediates

Methods For Preparing Higher Diamondoid Derivatives and Intermediates

Polymerization of Higher Diamondoid Derivatives

Higher Diamondoid-Containing Polymers

Utility

Definitions

As used herein, the following terms have the following meanings.

The term “diamondoid” refers to substituted and unsubstituted cagedcompounds of the adamantane series including substituted andunsubstituted adamantane, diamantane, triamantane, tetramantane,pentamantane, hexamantane, heptamantane, octamantane, nonamantane,decamantane, undecamantane, and the like and also including variousmolecular weight forms of these components and including isomers ofthese forms. Substituted diamondoids preferably comprise from 1 to 10and more preferably 1 to 4 alkyl substituents. “Diamondoids” include“lower diamondoids” and “higher diamondoids”.

The term “lower diamondoids” or “adamantane, diamantane and triamantane”refers to any and/or all unsubstituted and substituted derivatives ofadamantane, diamantane or triamantane. These lower diamondoids show noisomers and are readily synthesized, distinguishing them from the“higher diamondoids”.

The term “higher diamondoids” refers to any and/or all substituted andunsubstituted tetramantanes; to any and/or all substituted andunsubstituted pentamantanes; to any and/or all substituted andunsubstituted hexamantanes; to any and/or all substituted andunsubstituted heptamantanes; to any and/or all substituted andunsubstituted octamantanes; to any and/or all substituted andunsubstituted nonamantanes; to any and/or all substituted andunsubstituted decamantanes; to any and/or all substituted andunsubstituted undecamantanes; as well as mixtures of the above as wellas isomers and stereoisomers. When reference is being made to one ormore specific higher diamondoid isomers, they will often be referred toas “component” or “components”, for example a “tetramantane component.”

The term “higher diamondoid derivative” refers to a higher diamondoidwhich has had at least one of its hydrogens replaced by a polymerizablemoiety. The portion of the higher diamondoid present in a higherdiamondoid derivative is referred to as a “higher diamondoid nucleus.”

The term “polymerizable moiety” refers to any chemical functional groupthat, when covalently attached to a higher diamondoid, can participatein a polymerization reaction to form a polymer or can participate in thecovalent attachment of the diamondoid to a polymer substrate. Suchgroups include, without limitation, the following: unsaturated esters,amides, epoxides, alkenes, alkynes, amines, hydroxyls, and carboxyls.Preferably, the polymerizable moiety is an alkene, an unsaturated esteror an amide.

The term “higher diamondoid intermediate” refers to a higher diamondoidwhich has had at least one of its hydrogens replaced by an “intermediatemoiety.”

The term “intermediate moiety” refers to any chemical functional groupthat, when covalently attached to a higher diamondoid, can either serveas a polymerizable moiety or as an intermediate in the synthesis of apolymerizable moiety on the higher diamondoid.

The terms “conditions suitable for inducing a polymerization reaction”,“suitable polymerization conditions” and the like refer to any chemicalreaction parameters that will allow at least one polymerizable higherdiamondoid derivative to form a covalent bond with another, or with apolymer substrate.

The terms “polymer” and “higher diamondoid-containing polymer” and thelike refer to a molecule having multiple copies of the same or differenthigher diamondoid nucleus, covalently attached to each other or to abackbone chain. This includes polymers where the higher diamondoidnucleus is pendant from and not part of the polymer chain includingatactic ard isotactic polymers and polymers where a higher diamondoidnucleus is part of the polymer chain. FIGS. 4 and 35-41 show a varietyof representative polymer structures of this invention. “Polymers”include “homopolymers” and “copolymers” and “terpolymers.” A unit orgroup, whether higher diamondoid or other, which reports in a polymer issaid to “recur” to be a “recurring unit” of the polymer.

The term “homopolymer” refers to a polymer having only higher diamondoidrecurring units. For the purposes of this specification and claimshomopolymers will also include polymers having two or more differenthigher diamondoid recurring units.

The term “copolymer” refers to a polymer formed from one or more higherdiamondoid derivative and an additional nondiamondoid monomer and thushaving higher diamondoid and nondiamondoid recurring units.

The term “terpolymer” refers a polymer formed from one or more higherdiamondoid derivatives and two or more nondiamondoid monomers.

The term “linker” refers to a nondiamondoid moiety having at least 2 andpreferably 2-10 identical or different functional groups. At least oneof the functional groups reacts with at least one polymerizable moietyor intermediate moiety on the higher diamondoid derivative. At least oneadditional functional group takes part in the polymerization reaction.

The term “a polymerization reaction” refers to the reaction of a higherdiamondoid derivative performed under suitable polymerization conditionsto form a polymer.

The term “feedstock” or “hydrocarbonaceous feedstock” refers tohydro-carbonaceous materials comprising recoverable amounts of higherdiamondoids. Preferably, such feedstocks include oil, gas condensates,refinery streams, oils derived from reservoir rocks, oil shale, tarsands, and source rocks, and the like. Such components typically, butnot necessarily, comprise one or more lower diamondoid components aswell as nondiamondoid components. The latter is typically characterizedas comprising components having a boiling point both below and above thelowest boiling point tetramantane which boils at about 350° C. atatmospheric pressure. Typical feedstocks may also contain impuritiessuch as sediment, metals including nickel, vanadium and otherinorganics. They may also contain heteromolecules containing sulfur,nitrogen and the like. All of these nondiamondoid materials are includedin “nondiamondoid components” as that term is defined herein.

The term “nondiamondoid components” refers to components of thefeedstock from which diamondoids are isolated that are not diamondoid incharacter wherein the term “diamondoid” is as defined herein.

The term “chromatography” refers to any of a number of well knownchromatographic techniques including, by way of example only, column orgravity chromatography (either normal or reverse phase), gaschromatography (GC), high performance liquid chromatography (HPLC), andthe like.

The term “alkyl” refers to straight and branched chain saturatedaliphatic groups typically having from 1 to 20 carbon atoms, morepreferably 1 to 6 atoms (“lower alkyls”), as well as cyclic saturatedaliphatic groups typically having from 3 to 20 carbon atoms andpreferably from 3 to 6 carbon atoms (“lower alkyls” as well). The terms“alkyl” and “lower alkyl” are exemplified by groups such as methyl,ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, t-butyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The term “substituted alkyl” refers to an alkyl group as defined above,having from 1 to 5 substituents, and preferably 1 to 3 substituents,selected from the group consisting of alkoxy, substituted alkoxy,cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, acyl, acylamino, acyloxy, amino, substituted amino,aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl,keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy,thioheterocyclooxy, thiol, thioalkoxy, substituted thioalkoxy, aryl,aryloxy, heteroaryl, heteroaryloxy, heterocyclic, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-substituted alkyl,—SO-aryl, —SO-heteroaryl, —SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryland —SO₂-heteroaryl.

The term “alkylene” refers to a divalent (branched or unbranched)saturated hydrocarbon chain, preferably having from 1 to 40 carbonatoms, more preferably 1 to 10 carbon atoms and even more preferably 1to 6 carbon atoms. This term is exemplified by groups such as methylene(—CH₂—), ethylene (—CH₂CH₂—), the propylene isomers (e.g., —CH₂CH₂CH₂—and —CH(CH₃)CH₂—) and the like.

The term “substituted alkylene” refers to an alkylene group, as definedabove, having from 1 to 5 substituents, and preferably 1 to 3substituents, selected from the group consisting of alkoxy, substitutedalkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, acyl, acylamino, acyloxy, amino, substituted amino,aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl,keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy,thioheterocyclooxy, thiol, thioalkoxy, substituted thioalkoxy, aryl,aryloxy, heteroaryl, heteroaryloxy, heterocyclic, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-substituted alkyl,—SO-aryl, —SO-heteroaryl, —SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryland —SO₂-heteroaryl. Additionally, such substituted alkylene groupsinclude those where 2 substituents on the alkylene group are fused toform one or more cycloalkyl, substituted cycloalkyl, cycloalkenyl,substituted cycloalkenyl, aryl, heterocyclic or heteroaryl groups fusedto the alkylene group. Preferably such fused groups contain from 1 to 3fused ring structures.

The term “alkaryl” refers to the groups -alkylene-aryl and -substitutedalkylene-aryl where alkylene, substituted alkylene and aryl are definedherein. Such alkaryl groups are exemplified by benzyl, phenethyl and thelike.

The term “alkoxy” refers to the groups alkyl-O—, alkenyl-O—,cycloalkyl-O—, cycloalkenyl-O—, and alkynyl-O—, where alkyl, alkenyl,cycloalkyl, cycloalkenyl, and alkynyl are as defined herein. Preferredalkoxy groups are alkyl-O— and include, by way of example, methoxy,ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, sec-butoxy,n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like.

The term “substituted alkoxy” refers to the groups substituted alkyl-O—,substituted alkenyl-O—, substituted cycloalkyl-O—, substitutedcycloalkenyl-O—, and substituted alkynyl-O— where substituted alkyl,substituted alkenyl, substituted cycloalkyl, substituted cycloalkenyland substituted alkynyl are as defined herein.

The term “alkylalkoxy” refers to the groups -alkylene-O-alkyl,alkylene-O-substituted alkyl, substituted alkylene-O-alkyl andsubstituted alkylene-O-substituted alkyl wherein alkyl, substitutedalkyl, alkylene and substituted alkylene are as defined herein.Preferred alkylalkoxy groups are alkylene-O-alkyl and include, by way ofexample, methylenemethoxy (—CH₂OCH₃), ethylenemethoxy (—CH₂CH₂OCH₃),n-propylene-iso-propoxy (—CH₂CH₂CH₂OCH(CH₃)₂), methylene-t-butoxy(—CH₂—O—C(CH₃)₃) and the like.

The term “alkylthioalkoxy” refers to the group -alkylene-S-alkyl,alkylene-S-substituted alkyl, substituted alkylene-S-alkyl andsubstituted alkylene-S-substituted alkyl wherein alkyl, substitutedalkyl, alkylene and substituted alkylene are as defined herein.Preferred alkylthioalkoxy groups are alkylene-S-alkyl and include, byway of example, methylenethiomethoxy (—CH₂SCH₃), ethylenethiomethoxy(—CH₂CH₂SCH₃), n-propylene-iso-thiopropoxy (—CH₂CH₂CH₂SCH(CH₃)₂),methylene-t-thiobutoxy (—CH₂SC(CH₃)₃) and the like.

The term “alkenyl” refers to a monovalent of a branched or unbranchedunsaturated hydrocarbon group preferably having from 2 to 40 carbonatoms, more preferably 2 to 10 carbon atoms and even more preferably 2to 6 carbon atoms and having at least 1 and preferably from 1-6 sites ofvinyl unsaturation. Preferred alkenyl groups include ethenyl (—CH═CH₂),n-propenyl(—CH₂CH═CH₂), iso-propenyl (—C(CH₃)═CH₂), and the like.

The term “substituted alkenyl” refers to an alkenyl group as definedabove having from 1 to 5 substituents, and preferably 1 to 3substituents, selected from the group consisting of alkoxy, substitutedalkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, acyl, acylamino, acyloxy, amino, substituted amino,aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl,keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy,thioheterocyclooxy, thiol, thioalkoxy, substituted thioalkoxy, aryl,aryloxy, heteroaryl, heteroaryloxy, heterocyclic, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-substituted alkyl,—SO-aryl, —SO-heteroaryl, —SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryland —SO₂-heteroaryl.

The term “alkenylene” refers to a divalent of a branched or unbranchedunsaturated hydrocarbon group preferably having from 2 to 40 carbonatoms, more preferably 2 to 10 carbon atoms and even more preferably 2to 6 carbon atoms and having at least 1 and preferably from 1-6 sites ofvinyl unsaturation. This term is exemplified by groups such asethenylene (—CH═CH—), the propenylene isomers (e.g., —CH₂CH═CH— and—C(CH₃)═CH—) and the like.

The term “substituted alkenylene” refers to an alkenylene group asdefined above having from 1 to 5 substituents, and preferably from 1 to3 substituents, selected from the group consisting of alkoxy,substituted alkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl,substituted cycloalkenyl, acyl, acylamino, acyloxy, amino, substitutedamino, aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen,hydroxyl, keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy,thioheteroaryloxy, thioheterocyclooxy, thiol, thioalkoxy, substitutedthioalkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocyclic,heterocyclooxy, hydroxyamino, alkoxyamino, nitro, —SO-alkyl,—SO-substituted alkyl, —SO-aryl, —SO-heteroaryl, —SO₂-alkyl,—SO₂-substituted alkyl, —SO₂-aryl and —SO₂-heteroaryl. Additionally,such substituted alkenylene groups include those where 2 substituents onthe alkenylene group are fused to form one or more cycloalkyl,substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, aryl,heterocyclic or heteroaryl groups fused to the alkenylene group.

The term “alkynyl” refers to a monovalent unsaturated hydrocarbonpreferably having from 2 to 40 carbon atoms, more preferably 2 to 20carbon atoms and even more preferably 2 to 6 carbon atoms and having atleast 1 and preferably from 1-6 sites of acetylene (triple bond)unsaturation. Preferred alkynyl groups include ethynyl (—C≡CH),propargyl (—CH₂C≡CH) and the like.

The term “substituted alkynyl” refers to an alkynyl group as definedabove having from 1 to 5 substituents, and preferably 1 to 3substituents, selected from the group consisting of alkoxy, substitutedalkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, acyl, acylamino, acyloxy, amino, substituted amino,aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl,keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy,thioheterocyclooxy, thiol, thioalkoxy, substituted thioalkoxy, aryl,aryloxy, heteroaryl, heteroaryloxy, heterocyclic, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-substituted alkyl,—SO-aryl, —SO-heteroaryl, —SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryland —SO₂-heteroaryl.

The term “alkynylene” refers to a divalent unsaturated hydrocarbonpreferably having from 2 to 40 carbon atoms, more preferably 2 to 10carbon atoms and even more preferably 2 to 6 carbon atoms and having atleast 1 and preferably from 1-6 sites of acetylene (triple bond)unsaturation. Preferred alkynylene groups include ethynylene (—C≡C—),propargylene (—CH₂C≡C—) and the like.

The term “substituted alkynylene” refers to an alkynylene group asdefined above having from 1 to 5 substituents, and preferably 1 to 3substituents, selected from the group consisting of alkoxy, substitutedalkoxy, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, acyl, acylamino, acyloxy, amino, substituted amino,aminoacyl, aminoacyloxy, oxyaminoacyl, azido, cyano, halogen, hydroxyl,keto, thioketo, carboxyl, carboxylalkyl, thioaryloxy, thioheteroaryloxy,thioheterocyclooxy, thiol, thioalkoxy, substituted thioalkoxy, aryl,aryloxy, heteroaryl, heteroaryloxy, heterocyclic, heterocyclooxy,hydroxyamino, alkoxyamino, nitro, —SO-alkyl, —SO-substituted alkyl,—SO-aryl, —SO-heteroaryl, —SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryland —SO₂-heteroaryl.

The term “acyl” refers to the groups HC(O)—, alkyl-C(O)—, substitutedalkyl-C(O)—, cycloalkyl-C(O)—, substituted cycloalkyl-C(O)—,cycloalkenyl-C(O)—, substituted cycloalkenyl-C(O)—, aryl-C(O)—,heteroaryl-C(O)— and heterocyclic-C(O)— where alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, cycloalkenyl, substitutedcycloalkenyl, aryl, heteroaryl and heterocyclic are as defined herein.

The term “acylamino” or “aminocarbonyl” refers to the group —C(O)NRRwhere each R is independently hydrogen, alkyl, substituted alkyl, aryl,heteroaryl, heterocyclic or where both R groups are joined to form aheterocyclic group (e.g., morpholino) wherein alkyl, substituted alkyl,aryl, heteroaryl and heterocyclic are as defined herein.

The term “aminoacyl” refers to the group —NRC(O)R where each R isindependently hydrogen, alkyl, substituted alkyl, aryl, heteroaryl, orheterocyclic wherein alkyl, substituted alkyl, aryl, heteroaryl andheterocyclic are as defined herein.

The term “aminoacyloxy” or “alkoxycarbonylamino” refers to the group—NRC(O)OR where each R is independently hydrogen, alkyl, substitutedalkyl, aryl, heteroaryl, or heterocyclic wherein alkyl, substitutedalkyl, aryl, heteroaryl and heterocyclic are as defined herein.

The term “acyloxy” refers to the groups alkyl-C(O)O—, substitutedalkyl-C(O)O—, cycloalkyl-C(O)O—, substituted cycloalkyl-C(O)O—,aryl-C(O)O—, heteroaryl-C(O)O—, and heterocyclic-C(O)O— wherein alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, heteroaryl,and heterocyclic are as defined herein.

The term “aryl” refers to an unsaturated aromatic carbocyclic group offrom 6 to 20 carbon atoms having a single ring (e.g., phenyl) ormultiple condensed (fused) rings (e.g., naphthyl or anthryl). Preferredaryls include phenyl, naphthyl and the like.

Unless otherwise constrained by the definition for the aryl substituent,such aryl groups can optionally be substituted with from 1 to 5substituents, preferably 1 to 3 substituents, selected from the groupconsisting of acyloxy, hydroxy, thiol, acyl, alkyl, alkoxy, alkenyl,alkynyl, cycloalkyl, cycloalkenyl, substituted alkyl, substitutedalkoxy, substituted alkenyl, substituted alkynyl, substitutedcycloalkyl, substituted cycloalkenyl, amino, substituted amino,aminoacyl, acylamino, alkaryl, aryl, aryloxy, azido, carboxyl,carboxylalkyl, cyano, halo, nitro, heteroaryl, heteroaryloxy,heterocyclic, heterocyclooxy, aminoacyloxy, oxyacylamino, thioalkoxy,substituted thioalkoxy, thioaryloxy, thioheteroaryloxy, —SO-alkyl,—SO-substituted alkyl, —SO-aryl, —SO-heteroaryl, —SO₂-alkyl,—SO₂-substituted alkyl, —SO₂-aryl, —SO₂-heteroaryl and trihalomethyl.Preferred aryl substituents include alkyl, alkoxy, halo, cyano, nitro,trihalomethyl, and thioalkoxy.

The term “aryloxy” refers to the group aryl-O— wherein the aryl group isas defined above including optionally substituted aryl groups as alsodefined above.

The term “arylene” refers to the divalent derived from aryl (includingsubstituted aryl) as defined above and is exemplified by 1,2-phenylene,1,3-phenylene, 1,4-phenylene, 1,2-naphthylene and the like.

The term “amino” refers to the group —NH₂.

The term “substituted amino” refers to the group —NRR where each R isindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl,substituted alkynyl, aryl, heteroaryl and heterocyclic provided thatboth R′s are not hydrogen.

The term “carboxyalkyl” or “alkoxycarbonyl” refers to the groups“—C(O)O-alkyl”, “—C(O)O-substituted alkyl”, “—C(O)β-cycloalkyl”,“—C(O)O-substituted cycloalkyl”, “—C(O)O-alkenyl”, “—(O)O-substitutedalkenyl”, “—C(O)O-alkynyl” and “—C(O)O-substituted alkynyl” where alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,substituted alkenyl, alkynyl and substituted alkynyl are as definedherein.

The term “cycloalkyl” refers to cyclic alkyl groups of from 3 to 20carbon atoms having a single cyclic ring or multiple condensed rings.Such cycloalkyl groups include, by way of example, single ringstructures such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, andthe like, or multiple ring structures such as adamantanyl, and the like.

The term “substituted cycloalkyl” refers to cycloalkyl groups havingfrom 1 to 5 substituents, and preferably 1 to 3 substituents, selectedfrom the group consisting of alkoxy, substituted alkoxy, cycloalkyl,substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, acyl,acylamino, acyloxy, amino, substituted amino, aminoacyl, aminoacyloxy,oxyaminoacyl, azido, cyano, halogen, hydroxyl, keto, thioketo, carboxyl,carboxylalkyl, thioaryloxy, thioheteroaryloxy, thioheterocyclooxy,thiol, thioalkoxy, substituted thioalkoxy, aryl, aryloxy, heteroaryl,heteroaryloxy, heterocyclic, heterocyclooxy, hydroxyamino, alkoxyamino,nitro, —SO-alkyl, —SO-substituted alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryl and —SO₂-heteroaryl.

The term “cycloalkenyl” refers to cyclic alkenyl groups of from 4 to 20carbon atoms having a single cyclic ring and at least one point ofinternal unsaturation. Examples of suitable cycloalkenyl groups include,for instance, cyclobut-2-enyl, cyclopent-3-enyl, cyclooct-3-enyl and thelike.

The term “substituted cycloalkenyl” refers to cycloalkenyl groups havingfrom 1 to 5 substituents, and preferably 1 to 3 substituents, selectedfrom the group consisting of alkoxy, substituted alkoxy, cycloalkyl,substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, acyl,acylamino, acyloxy, amino, substituted amino, aminoacyl, aminoacyloxy,oxyaminoacyl, azido, cyano, halogen, hydroxyl, keto, thioketo, carboxyl,carboxylalkyl, thioaryloxy, thioheteroaryloxy, thioheterocyclooxy,thiol, thioalkoxy, substituted thioalkoxy, aryl, aryloxy, heteroaryl,heteroaryloxy, heterocyclic, heterocyclooxy, hydroxyamino, alkoxyamino,nitro, —SO-alkyl, —SO-substituted alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryl and —SO₂-heteroaryl.

The term “halo” or “halogen” refers to fluoro, chloro, bromo and iodo.

The term “heteroaryl” refers to an aromatic group of from 1 to 15 carbonatoms and 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfurwithin at least one ring (if there is more than one ring).

Unless otherwise constrained by the definition for the heteroarylsubstituent, such heteroaryl groups can be optionally substituted with 1to 5 substituents, preferably 1 to 3 substituents, selected from thegroup consisting of acyloxy, hydroxy, thiol, acyl, alkyl, alkoxy,alkenyl, alkynyl, cycloalkyl, cycloalkenyl, substituted alkyl,substituted alkoxy, substituted alkenyl, substituted alkynyl,substituted cycloalkyl, substituted cycloalkenyl, amino, substitutedamino, aminoacyl, acylamino, alkaryl, aryl, aryloxy, azido, carboxyl,carboxylalkyl, cyano, halo, nitro, heteroaryl, heteroaryloxy,heterocyclic, heterocyclooxy, aminoacyloxy, oxyacylamino, thioalkoxy,substituted thioalkoxy, thioaryloxy, thioheteroaryloxy, —SO-alkyl,—SO-substituted alkyl, —SO-aryl, —SO-heteroaryl, —SO₂-alkyl,—SO₂-substituted alkyl, —SO₂-alkyl, —SO₂-heteroaryl and trihalomethyl.Preferred aryl substituents include alkyl, alkoxy, halo, cyano, nitro,trihalomethyl, and thioalkoxy. Such heteroaryl groups can have a singlering (e.g., pyridyl or furyl) or multiple condensed rings (e.g.,indolizinyl or benzothienyl). Preferred heteroaryls include pyridyl,pyrrolyl and furyl.

The term “heteroaryloxy” refers to the group heteroaryl-O—.

The term “heteroarylene” refers to the divalent group derived fromheteroaryl (including substituted heteroaryl), as defined above, and isexemplified by the groups 2,6-pyridylene, 2,4-pyridiylene,1,2-quinolinylene, 1,8-quinolinylene, 1,4-benzofuranylene,2,5-pyridnylene, 2,5-indolenyl and the like.

The term “alkheteroaryl” refers to the group -alkylene-heteroaryl wherealkylene and heteroaryl are as defined herein.

The term “alkheteroarylene” refers to the group -alkylene-heteroarylenewhere alkylene and heteroarylene are as defined herein.

The term “heterocycle” or “heterocyclic” refers to a monovalentsaturated unsaturated group having a single ring or multiple condensedrings, from 1 to 40 carbon atoms and from 1 to 10 hetero atoms,preferably 1 to 4 heteroatoms, selected from nitrogen, sulfur,phosphorus, and/or oxygen within the ring.

Unless otherwise constrained by the definition for the heterocyclicsubstituent, such heterocyclic groups can be optionally substituted with1 to 5, and preferably 1 to 3 substituents, selected from the groupconsisting of alkoxy, substituted alkoxy, cycloalkyl, substitutedcycloalkyl, cycloalkenyl, substituted cycloalkenyl, acyl, acylamino,acyloxy, amino, substituted amino, aminoacyl, aminoacyloxy,oxyaminoacyl, azido, cyano, halogen, hydroxyl, keto, thioketo, carboxyl,carboxylalkyl, thioaryloxy, thioheteroaryloxy, thioheterocyclooxy,thiol, thioalkoxy, substituted thioalkoxy, aryl, aryloxy, heteroaryl,heteroaryloxy, heterocyclic, heterocyclooxy, hydroxyamino, alkoxyamino,nitro, —SO-alkyl, —SO-substituted alkyl, —SO-aryl, —SO-heteroaryl,—SO₂-alkyl, —SO₂-substituted alkyl, —SO₂-aryl and —SO₂-heteroaryl. Suchheterocyclic groups can have a single ring or multiple condensed rings.Preferred heterocyclics include morpholino, piperidinyl, and the like.

Examples of nitrogen heterocycles and heteroaryls include, but are notlimited to, pyrrole, imidazole, pyrazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthylpyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,phenanthridine, acridine, phenanthroline, isothiazole, phenazine,isoxazole, phenoxazine, phenothiazine, imidazolidine, imidazoline,piperidine, piperazine, indoline, morpholino, piperidinyl,tetrahydrofuranyl, and the like as well as N-alkoxy-nitrogen containingheterocycles.

The term “heterocyclooxy” refers to the group heterocyclic-O—.

The term “thioheterocyclooxy” refers to the group heterocyclic-S—.

The term “heterocyclene” refers to the divalent group formed from aheterocycle, as defined herein, and is exemplified by the groups2,6-morpholino, 2,5-morpholino and the like.

The term “oxyacylamino” or “aminocarbonyloxy” refers to the group—OC(O)NRR where each R is independently hydrogen, alkyl, substitutedalkyl, aryl, heteroaryl, or heterocyclic wherein alkyl, substitutedalkyl, aryl, heteroaryl and heterocyclic are as defined herein.

The term “spiro-attached cycloalkyl group” refers to a cycloalkyl groupattached to another ring via one carbon atom common to both rings.

The term “thiol” refers to the group —SH.

The term “thioalkoxy” refers to the group —S-alkyl.

The term “substituted thioalkoxy” refers to the group —S-substitutedalkyl.

The term “thioaryloxy” refers to the group aryl-S— wherein the arylgroup is as defined above including optionally substituted aryl groupsalso defined above.

The term “thioheteroaryloxy” refers to the group heteroaryl-S— whereinthe heteroaryl group is as defined above including optionallysubstituted aryl groups as also defined above.

As to any of the above groups which contain one or more substituents, itis understood, of course, that such groups do not contain anysubstitution or substitution patterns which are sterically impracticaland/or synthetically non-feasible. In addition, the compounds of thisinvention include all stereochemical isomers arising from thesubstitution of these compounds.

Higher Diamondoids and Their Recovery

As shown in FIG. 1A, higher diamondoids are bridged-ring cycloalkanesthat have carbon-atom frameworks that can be superimposed on the diamondcrystal lattice. They are the tetramers, pentamers, hexamers, heptamers,octamers, nonamers, decamers, etc. of adamantane(tricyclo[3.3.1.1^(3,7)]decane) or C₁₀H₁₆ in which various adamantaneunits are face-fused. The higher diamondoids can contain many alkylsubstituents. These compounds have extremely rigid structures and havethe highest stability of any compound with their formula. There are fourtetramantane structures; iso-tetramantane [1(2)3], anti-tetramantane[121] and two enantiomers of skew-tetramantane [123] with the moregeneral bracketed nomenclature for these diamondoids in accordance to aconvention by Balaban et al.¹⁵ There are ten pentamantanes, nine havethe molecular formula C₂₆H₃₂ (molecular weight 344), and among thesenine there are three pairs of enantiomers represented by: [12(1)3],[1234], [1213] with the non-enantiomeric pentamantanes represented by:[12(3)4], [1(2,3)4], [1212]. There also exists a more strainedpentamantane, [1231], represented by the molecular formula C₂₅H₃₀(molecular weight 330). Hexamantanes exist with thirty-nine differentstructures, twenty-eight having the molecular formula C₃₀H₃₆ (molecularweight 396) and of these, six are achiral; ten more strainedhexamantanes have the molecular formula C₂₉H₃₄ (molecular weight 382)and the remaining hexamantane [12312] has the molecular formula C₂₆H₃₀(molecular weight 342), also called cyclohexamantane because of itshighly condensed circular structure. Heptamantanes are postulated toexist in one hundred and sixty possible structures; with eighty-fivehaving the molecular formula C₃₄H₄₀ (molecular weight 448) and of these,seven are achiral, having no enantiomers. Of the heptamantanes,sixty-seven have the molecular formula C₃₃H₃₈ (molecular weight 434),and six have the molecular formula C₃₂H₃₆ (molecular weight 420). Thesetwo heptamantane families have structures showing greater internal bondstrain, with correspondingly lower stabilities. The remaining two havethe molecular formula C₃₀H₃₄ (molecular weight 394). Octamantanespossess eight of the “diamond crystal cage units” and exist within fivefamilies of different molecular weight core structures. Among theoctamantanes, eighteen have the molecular formula C₃₄H₃₈ (molecularweight 446). Other octamantanes have the molecular formula C₃₈H₄₄(molecular weight 500). The remaining octamantane families, C₃₇H₄₂(molecular weight 486), C₃₆H₄₀ (molecular weight 472) and C₃₃H₃₆(molecular weight 432) show greater bond strain and correspondinglylower stability. Nonamantanes exist within six families of differentmolecular weights having the following molecular formulas: C₄₂H₄₈(molecular weight 552), C₄₁H₄₆ (molecular weight 538), C₄₀H₄₄ (molecularweight 524), C₃₈H₄₂ (molecular weight 498), C₃₇H₄₀ (molecular weight484) and C₃₄H₃₆ (molecular weight 444). Additionally, decamantane existswithin families of seven different molecular weights. Among thedecamantanes, there is a single decamantane having the molecular formulaC₃₅H₃₆ (molecular weight 456) which is structurally compact in relationto the other decamantanes and has low internal bond strain. The otherdecamantane families have the molecular formulas: C₄₆H₅₂ (molecularweight 604), C₄₅H₅₀ (molecular weight 590), C₄₄H₄₈ (molecular weight576), C₄₂H₄₆ (molecular weight 550), C₄₁H₄₄ (molecular weight 536) andC₃₈H₄₀ (molecular weight 496). Undecamantanes exist as molecularformulas C₅₀H₅₆ (molecular weight 656), C₄₉H₅₄ (molecular weight 642),C₄₈H₅₂ (molecular weight 628), C₄₆H₅₀ (molecular weight 602), C₄₅H₄₈(molecular weight 588), C₄₂H₄₄ (molecular weight 548), C₄₁H₄₂ (molecularweight 534), C₃₉H₄₀ (molecular weight 508). More preferred and lesspreferred higher diamondoids are based on their internal bond strain andcorresponding stabilities which is reflected by their relativeconcentrations in the various feedstocks. FIG. 1B shows examples ofhigher diamondoid monomer structures (tetramantanes to undecamantanes)that contain one or two derivative (R) groups useful for polymerpreparation. FIG. 1B gives examples showing that higher diamondoids havea great variety of shapes, dimensions and attachment sites for R groups.These variations will have significant effects in determining theproperties of the polymers they will form. Also, FIGS. 5D-5F indicatethat the rigidity of polymer structures formed from higher diamondoidmonomers will vary greatly with the attachment sites of R groups on themonomers.

FIG. 2A shows a representative carbon-numbering scheme for atetramantane, in which the quaternary, tertiary, and secondary carbonsare highlighted. Carbon numbering schemes for several representativehigher diamondoids are illustrated in FIGS. 2B-2F.

After numbering the carbons atoms in a higher diamondoid, adetermination of the number of equivalent tertiary and secondary carbonscan be made. This can be based upon observations of molecular symmetryor it can be based upon computerized simulations of Nuclear MagneticResonance (NMR) spectra, which correlate with the symmetry of the cagedmolecule, i.e., equivalent carbons have identical NMR chemical shifts.FIG. 2B shows the structures of the four different tetramantanes. Eachcarbon is numbered. As shown, these tetramantanes have different numbersof equivalent and non-equivalent tertiary carbons.

FIG. 2C-2F show some examples of pentamantane, hexamantane, octamantane,and undecamantane diamondoids, respectively, and the numbering of theirindividual carbon atoms.

The higher diamondoid families contain multiple isomers (includingstereoisomers) and substituted or derivatized diamondoids will typicallycontain one or more chiral centers. Higher diamondoids larger thantetramantane exist in forms with more than one molecular weight. Ifdesired, such compounds can be isolated as pure isomers or stereoisomers(e.g., as individual enantiomers or diastereomers, or asstereoisomer-enriched mixtures). Pure stereoisomers (or enrichedmixtures) may be prepared using, for example, crystallization, opticallyactive solvents or stereo-selective reagents well-known in the art.Alternatively, racemic mixtures of such compounds can be separatedusing, for example, chiral column chromatography, chiral resolvingagents and the like.

Higher diamondoids can be recovered from readily available feedstocksusing the following general methods and procedures. It will beappreciated that where typical or preferred process conditions (i.e.,reaction temperatures, times, solvents, pressures, etc.) are given,other process conditions can also be used unless otherwise stated.Optimum reaction conditions may vary with feedstocks, but suchconditions can be determined by one skilled in the art by routineoptimization procedures.

A feedstock is selected such that it comprises recoverable amounts ofhigher diamondoid components. Preferred feedstocks include, for example,natural gas condensates and refinery streams having high concentrationsof diamondoids. With regard to the latter, such refinery streams includehydrocarbonaceous streams recoverable from cracking processes,distillations, coking and the like. Particularly preferred feedstocksinclude condensate feedstocks recovered from the Norphlet Formation inthe Gulf of Mexico and from the LeDuc Formation in Canada. Thesefeedstocks contain approximately 0.3 weight percent higher diamondoids,as determined by GC and GC/MS. These feedstocks are light colored andhave API gravities in the 19 to 20° range.

The general isolation processes of higher diamondoids are shown in FIG.7.

In one embodiment, the removal of contaminants includes distillation ofthe feedstock to remove non-diamondoid components as well as lowerdiamondoid components and in some cases other nonselected higherdiamondoids having boiling points less than that of the lowest boilingpoint higher diamondoid component selected for recovery.

In a particularly preferred embodiment, the feedstock is distilled toprovide cuts above and below about 335° C., atmospheric equivalentboiling point and, more preferably, above and below about 345° C.atmospheric equivalent boiling point. In either instance, the lowercuts, which are enriched in lower diamondoids and low boiling pointnon-diamondoid components are taken overhead and discarded and thehigher boiling cut, which is enriched in higher diamondoids, isretained. It is understood, of course, that the temperature for the cutpoint during distillation is a function of pressure and that the abovetemperatures are referenced to atmospheric pressure. A reduced pressurewill result in a lower distillation temperature to achieve the same cutpoint whereas an elevated pressure will result in a higher distillationtemperature to achieve the same cut point. The correlation ofpressure/temperature from atmospheric distillation to either reducedpressure or elevated pressure distillation is well within the skill ofthe art.

Distillation can be operated to fractionate the feedstocks and provideseveral cuts in a temperature range of interest to provide the initialenrichment of the selected higher diamondoids or groups of selectedhigher diamondoids. The cuts, which are enriched in one or more selecteddiamondoids or a particular diamondoid component of interest, areretained and may require further purification. The following Tableillustrates representative fractionation points that may be used toenrich various higher diamondoids in overheads. In practice it may beadvantageous to make wider temperature range cuts which would oftencontain groups of higher diamondoids which could be separated togetherin subsequent separation steps.

Fractionation Points

Most Preferred Preferred Useful Lower Cut Higher Cut Lower Cut HigherCut Lower Cut Higher Cut Temperature Temperature Temperature TemperatureTemperature Temperature Higher Diamondoid (° C.) (° C.) (° C.) (° C.) (°C.) (° C.) Tetramantanes 349 382 330 400 300 430 Pentamantanes 385 427360 450 330 490 Cyclohexamantanes 393 466 365 500 330 550 Hexamantanes393 466 365 500 330 550 Heptamantanes 432 504 395 540 350 600Octamantanes 454 527 420 560 375 610 Nonamantanes 463 549 425 590 380650 Decamantanes 472 571 435 610 390 660 Undecamantanes 499 588 455 625400 675

It shall be understood that substituted higher diamondoids mayaccordingly shift these preferred cut-point temperatures to highertemperatures due to the addition of substituent groups. Additionaltemperature refinements will allow for higher purity cuts for thediamondoid of interest. FIG. 10 provides further illustrations of howfractionation can provide cuts enriched in individual or multiple higherdiamondoid components.

It will be further understood that fractionation can be stopped before aselected higher diamondoid is taken overhead. In this case the higherdiamondoid can be isolated from the fractionation bottoms.

Other processes for the removal of lower diamondoids, unselected higherdiamondoids, if any, and/or hydrocarbonaceous non-diamondoid componentsinclude, by way of example only, size separation techniques, evaporationeither under normal or reduced pressure, crystallization,chromatography, well head separators, reduced pressure and the like.Removal processes can utilize the larger sizes of the higher diamondoidsto effect separation of lower diamondoids therefrom. For example, sizeseparation techniques using membranes will allow a feedstock retained inthe membrane to selectively pass lower diamondoids across the membranebarrier provided that the pore size of the membrane barrier is selectedto differentiate between compounds having the size of higher diamondoidcomponents as compared to lower diamondoid components. The pore size ofmolecular sieves such as zeolites and the like can also be used toeffect size separation.

In a preferred embodiment, the removal process provides for a treatedfeedstock having a ratio of lower diamondoid components to higherdiamondoid components of no greater than 9:1; more preferably, nogreater than 2:1; and even more preferably, the ratio is no greater than1:1. Even more preferably, after removal of the lower diamondoidcomponent(s) from the feedstock, at least about 10%, more preferably atleast 50% and still more preferably at least 90% of the higherdiamondoid components are retained in the feedstock as compared to thatamount found in the feedstock prior to the removal.

When recovery of hexamantane and higher diamondoid components is desiredand when the feedstock contains non-diamondoid contaminants, thefeedstock will also be generally subjected to pyrolysis to effectremoval of at least a portion of the hydrocarbonaceous non-diamondoidcomponents from the feedstock. The pyrolysis effectively concentratesthe amount of higher diamondoids in the pyrolytically treated feedstockthereby rendering their recovery possible (FIG. 11).

Pyrolysis is effected by heating the feedstock under vacuum conditionsor in an inert atmosphere, at a temperature of at least about 390° C.and, preferably, from about 400 to about 550° C., more preferably fromabout 400 to about 450° C., and especially 410 to 430° C.; for a periodof time to effect pyrolysis of at least a portion of the non-diamondoidcomponents of the feedstock. The specific conditions employed areselected such that recoverable amounts of selected higher diamondoidcomponents are retained in the feedstock. The selection of suchconditions is well within the skill of the art.

Preferably, pyrolysis is continued for a sufficient period and at asufficiently high temperature to thermally degrade at least about 10% ofthe non-diamondoid components (more preferably at least about 50% andeven more preferably at least about 90%) from the pyrolytically treatedfeedstock based on the total weight of the non-diamondoid components inthe feedstock prior to pyrolysis.

In yet another preferred embodiment, after pyrolysis of the feedstock,at least about 10%, more preferably at least about 50%, and still morepreferably at least about 90% of the higher diamondoid components areretained in the feedstock after pyrolytic treatment compared to thatamount found in the feedstock prior to pyrolytic treatment.

In a preferred embodiment, removal of lower diamondoids and low boilingpoint hydrocarbonaceous non-diamondoid components from the feedstockprecedes pyrolytic treatment. However, it is understood, that the orderof these procedures can be inverted such that pyrolysis occurs prior toremoval of lower diamondoids from the feedstock.

The pyrolysis procedure, while a preferred embodiment, is not alwaysnecessary. This arises because the concentration of higher diamondoidscan be sufficiently high in certain feedstocks that the treatedfeedstock (after removal of the lower diamondoid components) can be useddirectly in purification techniques such as chromatography,crystallization, etc. to provide higher diamondoid components. However,when the concentration or purity of higher diamondoid components in thefeedstock is not at the level to effect such a recovery, then apyrolytic step should be employed.

Even when pyrolysis is employed, it is preferred to further purify therecovered feedstock using one or more purification techniques such aschromatography, crystallization, thermal diffusion techniques, zonerefining, progressive recrystalization, size separation and the like. Ina particularly preferred process, the recovered feedstock is firstsubjected to gravity column chromatography using silver nitrateimpregnated silica gel followed by HPLC using two different columns ofdiffering selectivities to isolate the selected diamondoids andcrystallization to provide crystals of the highly concentrated targethigher diamondoids. Where higher diamondoid concentrations are not highenough for crystallization to occur, further concentration by, forexample, preparative capillary gas chromatography may be necessary.

Enantioselective (chiral) stationary phases have been applied inchromatographic methods to effectuate further separations. Highperformance liquid chromatography methods also offer the possibility ofusing chiral solvents or additives to achieve resolution of enantiomers.

For example, separation of enantiomeric forms of the high diamondoidscan be achieved using several approaches. One such approach isspontaneous crystallization with resolution and mechanical separation.This approach to enantiomer resolution can be enhanced by preparation ofderivatives or by the use of additives, chiral solvents, or varioustypes of seed crystals. Another resolution option is chemical separationunder kinetic or thermodynamic control. Other suitable processes forenantiomer resolution include chiral separations, which can be performedusing a gas chromatographic (GC) see “Chiral Chromatography”, T. E.Beesley, et. al, Wiley, Johnson & Sons, January 1998, incorporatedherein by references, by high performance liquid chromatographic (HPLC)and by supercritical fluid chromatographic (SFC) techniques, seeSupercritical fluids in Chromatography and Extraction”, R. M. Smith,Elsevier Science, December 1997, incorporated herein by references.

The examples illustrate methods for recovering various higherdiamondoids from the tetramantanes to the undecamantanes.

The Higher Diamondoid Derivatives

A higher diamondoid derivative is a higher diamondoid which has had atleast 1 and suitably from 1 to 6 of its hydrogens replaced by a covalentbond to a polymerizable moiety.

These higher diamondoid derivatives can be represented by Formula Ibelow:

wherein D is a higher diamondoid and, R¹, R², R³, R⁴, R⁵ and R⁶ areindependently selected from a group consisting of hydrogen and one ormore polymerizable moieties; provided there is at least onepolymerizable moiety on the compound. Preferably, the compound containseither one or two polymerizable moieties.

These preferred materials may be represented by Formulae IA and IBbelow:

in which R¹ or R¹ and R² are the same or different polymerizablemoieties. such as alkenyl, alkynyl, —OH, —C₂H₃O, —SH, —NH₂, —CO₂H,—C₆H₅, —C₆H₄NH₂, —C₆H₄CO₂H or —C₆H₄OH.

The higher diamondoid, D, may preferably be selected from the:tetramantanes, pentamantanes, hexamantanes, heptamantanes, octamantanes,nonamantanes, decamantanes, and undecamantanes. These higher diamondoidsmay be substituted or unsubstituted. Individual isolatedhigher-diamondoid components may be used as well as mixtures of isomersfrom a single higher diamondoid family as well as mixtures of materialsfrom several higher diamondoid families.

Of the higher diamondoids, the tetramantanes and pentamantanes are themost plentiful. The very high molecular weight materials such asdecamantanes and undecamantanes are the least plentiful. Each family canoffer unique structures and properties, however. Thus, whileavailability favors the tetramantanes and pentamantanes andhexamantanes, there may be compelling reasons to select others as well.

The polymerizable moieties which make up R¹—R⁶ can be selected fromgroups which can participate in a polymerization reaction. These includevinyls (alkenyls), alkynyls, epoxides, cyclic ethers sucil as ethoxites,hydroxyls, aldehyde, cyanos, siloxyls, cyanates, and the like.

These groups are capable of participating in addition polymerization,condensation polymerizations, and the like. In some cases, such as vinylpolymerizations, a single polymerizable group can form an additionpolymer. In other cases, two different polymerizable groups may need toreact with one another to effect polymerization, for example an acid andan amine reacting to form an amide-linked polymer.

Other examples of covalent bonds formed from complementary reactivegroups are documented in the art. Representative complimentary groupsare depicted in the Table 1.

TABLE 1 Complementary Polymerization Chemistries Diamondoid ReactiveGroup on Polymerizable Second Diamondoid Covalent Group Or Linking GroupLinkage Hydroxyl Isocyanoate Urethane Epoxide Hydroxyl Ether CarboxylAmine Amide Amine Carboxyl Amide Vinyl Vinyl Alkylene Thiol EpoxideThioether

In addition to these R groups, the polymerizable moieties can includegroups that are capable of linking the higher diamondoids to preformedpolymers. For example, an acid R¹—R⁶ group could react with an amine ona polymer to attach a higher diamondoid through an amide link. A widerange of moieties can serve this role. Examples of these latter R¹—R⁶groups include —F, —Cl, —Br, —I, —OH, —SH, —NH₂, —NHCOCH₃, —NHCHO,—CO₂H, —CO₂R′, —COCl, —CHO, —CH₂OH, ═O, —NO₂, —CH═CH₂, —C≡CH and —C₆H₅;where R′ is alkyl (preferably ethyl).

Suitable R¹—R⁶ groups may also be described by the following structure:—(X)_(m)—(Y)_(n)—Z, wherein X is —O—, —NR—, —OC(O)—, —NR⁸C(O)—, —C(O)O—or —C(O)NR⁹—, wherein R⁷, R⁸ and R⁹ are independently hydrogen or alkyl;Y is alkylene, arylene, alkarylene, heteroarylene or alkheteroarylene; Zis alkenyl, alkynyl, —OH, —C₂H₃O, —SH, —NH₂, —CO₂H, —C₆H₅, —C₆H₄NH₂,—C₆H₄CO₂H or —C₆H₄OH; m is 0 or 1; and n is 0 or 1.

Preferably, X is selected from a group consisting of —O—, —NR⁷— and—C(O)O—. Preferably, Z is selected from a group consisting of ethenyl,ethynyl, propenyl, propynyl, isobutenyl, butynyl, —NH₂, —CO₂H and —OH.

In one preferred embodiment, m and n are zero and Z is selected from agroup consisting of ethenyl, ethynyl, propenyl, propynyl, isobutenyl,butynyl, —NH₂, —C₂H₃O, —CO₂H, —OH and —SH.

In another preferred embodiment, Z is ethenyl, ethynyl, propenyl,propynyl, isobutenyl or butynyl, and X is —O—, —OC(O)— or —C(O)O— and mis 1 and n is 0.

In another preferred embodiment, Z is —OH, —NH₂, —C₂H₃O or —CO₂H, andmore preferably —NH₂, —C₂H₃O or —CO₂H, while m is 0, and Y is alkyleneor arylene.

In still another preferred embodiment, Z is —C₂H₃O or —SH, m is 0, and Yis alkylene.

Other preferred embodiments include, for instance: where Z is —C₆H₅,—C₆H₄NH₂, —C₆H₄CO₂H or —C₆H₄OH, m is 0, and n is 0. In another preferredembodiment Z is ethenyl, ethynyl, propenyl, propynyl, isobutenyl orbutynyl, m is one and X is —O—, —OC(O)— or —C(O)O—, and n is one and Yis —CH₂— or —(CH₂)₂—.

More preferred higher diamondoid derivatives include materials offormulae I and IA and IB wherein R¹ and R² are independently selectedfrom —F, —Cl, —Br, —I, —OH, —SH, —NH₂, —NHCOCH₃, —NHCHO, —CO₂H, —CO₂R′,—COCl, —CHO, —CH₂OH, ═O, —NO₂, —CH═CH₂, —C≡CH and —C₆H₅; where R′ isalkyl (preferably ethyl).

The Higher Diamondoid Intermediates

The higher diamondoid derivatives may often be formed going throughintermediates referred to as “higher diamondoid intermediates”. In somecases an intermediate may be polymerizable in its own right.

The higher diamondoid intermides may be represented by Formula II below:

wherein D is a higher diamondoid nucleus and at least one of R¹⁰—R¹⁵ isa covalently-attached moiety replacing a hydrogen which can be convertedto a polymerizable moiety or which, in some cases, may be apolymerizable moiety as well. The remaining R′s are hydrogens. Preferredintermediates have one or two nonhydrogen R′s and are represented byFormulae IIA and IIB:

wherein R¹⁰ and R¹¹ are nonhydrogen moieties capable of conversion topolymerizable moieties or capable of serving as polymerizable moieties.

In view of the broad definition of these intermediates, they can includethe polymerizable moieties defined above but alsc can include a widerange of halos, aldehydes, amines, alcohols, thiols, alkyls, aryls andthe like.

In Formulae II, IIA and IIB examples of R¹⁰—R¹⁵ include —H, —F, —Cl,—Br, —I, —OH, —SH, —NH₂, —NHCOCH₃, —NHCHO, —CO₂H, —CO₂R′, —COCl, —CHO,—CH₂OH, ═O, —NO₂, —CH═CH₂, —C≡CH and —C₆H₅; where R′ is alkyl(preferably ethyl) provided that R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and R¹⁵ are notall hydrogens.

These intermediates may be synthesized and isolated or may be present inreaction mixtures. In either event they are generally present inconcentrations of at least about 100 ppm and usually at least 1000 ppmor even greater, such as at least about 1% by weight.

Methods for Preparing of Higher Diamondoid Derivatives and Intermediates

There are two major reactions for the preparation of higher diamondoidderivatives and intermediates: nucleophilic (S_(N)1-type) andelectrophilic (S_(E)2-type) substitution reactions (details for suchreactions and their mechanisms for lower diamondoids, see, for instance,“Recent developments in the adamantane and related polycyclichydrocarbons” written by R. C. Bingham and P. v. R. Schleryer as a partof the book: “Chemistry of Adamantanes”, Springer-Verlag, BerlinHeidelberg, New York, 1971; “Reactions of adamantanes in electrophilicmedia” by I. K. Moiseev, N. V. Makarova, M. N. Zemtsova published inRussian Chemical Review, 68(12), 1001-1020 (1999); “Cage hydrocarbons”edited by George A. Olah, John Wiley & Son, Inc., New York, 1990).

S_(N)1 reactions involve the generation of higher diamondoidcarbocations, which subsequently react with various nucleophiles. Suchnucleophiles include, without limitation the following: water (providinghydroxylated higher diamondoids); halide ions (providing halogenatedhigher diamondoids); ammonia (providing aminated higher diamondoids);azide (providing azidylated higher diamondoids); nitriles (“Ritterreaction,” providing aminated higher diamondoids after hydrolysis);carbon monoxide (“Koch-Haaf reaction,” providing carboxylateddiamondoids after hydrolysis); olefins (providing alkenylated higherdiamondoids after deprotonation); and aromatic compounds (providingarylated higher diamondoids after deprotonation). The reactions occursimilarly to those of open chain alkyl systems, such as t-butyl, t-cumyland cycloalkyl systems. Since tertiary (bridgehead) carbons of higherdiamondoids are considerably more reactive than secondary carbons underS_(N)1 reaction conditions, substitution at the tertiary carbons isfavored.

An illustration of representative pathways by which higher diamondoidcarbocations are generated is shown in FIG. 3A, wherein D is a higherdiamondoid nucleus. Preferably the carbocation is generated from aparent higher diamondoid, a hydroxylated higher diamondoid intermediateor a halogenated higher diamondoid intermediate. FIG. 3B showsrepresentative S_(N)1 reaction pathways by which these higher diamondoidcarbocations can react to form higher diamondoid derivatives andintermediates. Intermediates expressed in the figures can be furtherderivatized (e.g., amide from amine or ester from alcohol) or reactedunder appropriate conditions to provide desired derivatives.

S_(E)2-type reactions (i.e., an electrophile substitution of a C—H bondvia a five-coordinate carbocation intermediate) include, but are notlimited to, the following reactions: hydrogen-deuterium exchange upontreatment with deuterated superacids (e.g., DF-SbF₅ or DSO₃F-SbF₅);nitration upon treatment with nitronium salts, such as NO₂ ⁺BF₄ ⁻ or NO₂⁺PF₆ ⁻ in the presence of superacids (e.g., CF₃SO₃H); halogenation upon,for instance, reaction with Cl₂+AgSbF₆; alkylation of the bridgeheadcarbons under Friedel-Crafts conditions (i.e., S_(E)2-type σalkylation); carboxylation under Koch reaction conditions; and,oxygenation under S_(E)2-type σ hydroxylation conditions (e.g., hydrogenperoxide or ozone using superacid catalysis involving H₃O₂ ⁺ or HO₃ ⁺,respectively). An illustration of representative pathways by whichhigher diamondoids are derivatized via eletrophilic substitutionreactions (S_(E)2 reactions) is shown in FIG. 3C.

Of the two major reactions for the derivatization of higher diamondoids,the S_(N)1-type is preferred.

Mono- and multi-brominated higher diamondoids are some of the mostversatile intermediates in the derivative chemistry of higherdiamondoids. These intermediates are used in, for example, theKoch-Haaf, Ritter, and Friedel-Crafts alkylation/arylation reactions.Brominated higher diamondoids are prepared by two different generalroutes. One involves direct bromination of the higher diamondoids orsubstituted higher diamondoids with elemental bromine in the presence orabsence of a Lewis acid (e.g. BBr₃—AlBr₃) catalyst. The other involvesthe substitution reaction of hydroxylated higher diamondoids withhydrobromic acid.

Direct bromination of higher diamondoids is highly selective, favoringsubstitution at the bridgehead (tertiary) carbons. By proper choice ofcatalyst and reaction conditions, one, two, three, four, or more brominemoieties can be introduced sequentially into the molecule, all atbridgehead positions. In the absence of a catalyst, the mono-bromoderivative is the major product with minor amounts of higher brominationproducts being formed. However, by use of suitable catalysts (e.g.,boron bromide and/or aluminum bromide), di-, tri-, tetra-, penta-, andhigher bromide derivatives of higher diamondoids are isolated as majorproducts in the bromination reaction. Typically, the tetrabromo orhigher bromo derivatives are synthesized at elevated temperatures in asealed tube.

Bromination reactions of higher diamondoids are usually terminated bypouring the reaction mixture onto ice or ice water and adding a suitableamount of chloroform, or ethyl ether, or carbon tetrachloride, to theice mixture. Excess bromine is then removed by distillation under vacuumwith the addition of solid sodium disulfide or sodium hydrogen sulfide.The organic layer is separated and the aqueous layer is extracted withchloroform, or ethyl ether, or carbon tetrachloride. This is repeated2-3 times. The resulting organic layers are then combined and washedwith aqueous sodium hydrogen carbonate and water, and dried.

To isolate the brominated derivatives, the solvent is typically removedunder vacuum. Typically, the reaction mixture is subjected to columnchromatography on either alumina or silica gel using standard elutionconditions (e.g., eluting with light petroleum ether, n-hexane, orcyclohexane, or mixtures thereof, with ethyl ether) to separate out thebromo higher diamondoid. Separation by preparative gas chromatography(GC) or high performance liquid chromatography (HPLC) can also be oftenused where normal column chromatography is difficult and/or the reactionis performed on extremely small quantities of material.

To prepare bromo derivatives where the bromos are present on secondarycarbons, for example, the corresponding hydroxylated higher diamondoidhydroxylated at the secondary sites is treated under mild conditionswith hydrobromic acid. Hydroxlyation of higher diamondoids is lessselective than bromination, allowing the preparation of compoundsfunctionalized at secondary carbons. Preferably, higher diamondoidshydroxylated at secondary carbons are prepared by the reduction of thecorresponding keto derivative.

For the general synthesis of higher diamondoid compounds substituted atsecondary carbons, free radical reactions are often employed. Thesetypes of reactions provide a higher ratio of secondary to tertiarysubstitution than do the nucleophilic reactions. Photochlorination is aparticularly useful free radical reaction, since chloro higherdiamondoid derivatives are similar to bromo compounds in reactivity.

Notwithstanding the above, several other reactions can be used tofunctionalize higher diamondoids. The following reactions areillustrative of some of these methods. For instance, higher diamondoidscan be halogenated in the following manner. As an example, fluorinationof a higher diamondoid is carried out by reacting the higher diamondoidwith a mixture of polyhydrogen fluoride and pyridine (30% Py, 70% HF) inthe presence of nitronium tetrafluoroborate. Sulfur tetrafluoride reactswith a higher diamondoid in the presence of sulfur monochloride toafford a mixture of mono-, di-, tri- and even higher fluorinated higherdiamondoids. Higher diamondoids are brominated upon treatment withbromine. This reaction can be carried out either in the presence orabsence of a Lewis acid (e.g., BBr₃—AlBr₃). Iodo higher diamondoids areobtained by a substitutive iodination of chloro, bromo or hydroxylhigher diamondoids.

Higher diamondoids can be functionaiized by other groups, they arenitrated by concentrated nitric acid in the presence of glacial aceticacid under high temperature and pressure. Higher diamondoidones aresynthesized by photooxidation in the presence of peracetic acid followedby treatment with chromic acid-sulfuric acid. Higher diamondoidones arereduced by, for instance, LiAlH₄, to hydroxylated higher diamondoids atthe secondary carbons. 2,2-bis(4-hydroxyphenyl) higher diamondoids or2,2-bis(4-aminophenyl) higher diamondoids are directly synthesized bythe acid-catalyzed (HCl-catalyzed) condensation of higher diamondoidoneswith excess phenol or aniline in the presence of hydrogen chloride.

Reaction of the brominated derivatives with hydrochloric acid indimethylformamide (DMF) converts the compounds to the correspondinghydroxylated derivatives. Brominated or iodinated higher diamondoids areconverted to thiolated higher diamondoids by way of, for instance,reacting with thioacetic acid to form higher diamondoid thioacetatesfollowed by removal of the acetate group under basic conditions. Theamino derivatives are also synthesized from the brominated derivativesby heating them in the presence of formamide and subsequentlyhydrolyzing the resultant amide.

Direct hydroxylation is also effected on higher diamondoids upontreatment with N-hydroxyphthalimide and a binary co-catalyst in aceticacid. The hydroxylated derivatives are esterified, for example, understandard conditions such as reaction with an activated acid derivative(e.g., CH₂═CHCOCl, CH₃CH═CHCOCl or (CH₃)₂C═CHCOCl). Alkylation isperformed on the hydroxylated compounds through nucleophilicdisplacement on an appropriate alkenyl halide (e.g., CH₂═CHCH₂Br,CH₃CH═CHCH₂Br or (CH₃)₂C═CHCH₂Br).

Similarly to the hydroxylated compounds, aminated higher diamonds areacylated or alkylated. For instance, reaction of an amino higherdiamondoid with an activated acid derivative produces the correspondingamide. Alkylation is typically performed by reacting the amine with asuitable carbonyl containing compound (e.g., CH₂═CH(CH₂)₃CHO) in thepresence of a reducing agent (e.g., sodium cyanoborohydride).

Carboxylated derivatives are obtained from the reaction of hydroxylatedderivatives with formic acid. The derivatives are esterified throughactivation (e.g., conversion to acid chloride) and subsequent exposureto an appropriate alcohol (e.g., CH₂═CHCH₂OH, CH₃CH═CHCH₂OH or(CH₃)₂C═CHCH₂OH). Amide formation is performed through activation of thecarboxylated derivative and reaction with a suitable amine (e.g.,CH₂═CHCH₂NH₂, CH₃CH═CHCH₂NH₂ or (CH₃)₂C═CHCH₂NH₂).

Ethenylated higher diamondoid derivatives are synthesized by reacting abrominated higher diamondoid with ethylene in the presence of AlBr₃followed by dehydrobromination with potassium hydroxide or the like. Theethenylated compound is transformed into the corresponding epoxide understandard reaction conditions (e.g., 3-chloroperbenzoic acid). Oxidativecleavage (e.g., ozonolysis) of the ethenylated higher diamondoid affordsthe related aldehyde. The ethynylated higher diamondoid derivatives areobtained by treating a brominated higher diamondoid with vinyl bromidein the presence of AlBr₃. The resultant product is dehydrohalogenatedusing potassium t-butoxide in dimethyl sulfoxide (DMSO) to provide thedesired compound.

The following table (Table 2) provides a representative list of higherdiamondoid intermediate groups that are used for the production ofpolymerizable higher diamondoid derivatives.

TABLE 2 Higher Diamondoid Intermediate Substituent Groups HIGHERDIAMONDOID SUBSTITUENT tetramantane - undecamantane F tetramantane -undecamantane Cl tetramantane - undecamantane Br tetramantane -undecamantane I tetramantane - undecamantane OH tetramantane -undecamantane CO₂H tetramantane - undecamantane CO₂CH₂CH₃ tetramantane -undecamantane COCl tetramantane - undecamantane SH tetramantane -undecamantane CHO tetramantane - undecamantane CH₂OH tetramantane -undecamantane NH₂ tetramantane - undecamantane NO₂ tetramantane -undecamantane. ═O (keto) tetramantane - undecamantane CH═CH₂tetramantane - undecamantane C≡CH tetramantane - undecamantane C₆H₅tetramantane - undecamantane NHCOCH₃ tetramantane - undecamantane NHCHOPolymerization of Higher Diamondoid Derivatives

Polymerizable higher diamondoid derivatives are subjected to suitablereaction conditions so that polymers, e.g., homopolymers or co-polymers,are produced. Polymerization is typically carried out using one of thefollowing different methods: free radical polymerization, cationicpolymerization, anionic polymerization or polycondensation reactions.

Free radical polymerization occurs spontaneously upon the absorption ofan adequate amount of heat, ultraviolet light or high-energy radiation.Typically, however, this polymerization process is induced by theaddition of a small amount of an initiator such as peroxides, azocompounds, Lewis acids ard organometallic agents. Examples of initiatorsinclude, without limitation, the following: aceyl and benzoyl peroxide,alkyl peroxides such as cumyl and t-butyl, hydroperoxides, peresters,azobisisobutyronitrile, di-t-butylperoxide and benzophenone.

Free radical polymerization can be conducted either on the underivatizedor derivatized higher diamondoid provided that the derivatized higherdiamondoid contains a functional group amenable to free radicalpolymerization. In the case of the underivatized higher diamondoid, orpreferably using a higher diamondoid derivative as the startingmaterial, such as a monobromo or dibromo substituted higher diamondoid,a covalent bond is formed between two of the higher diamondoidcomponents. Such a polymer formed can be represented generically by(D)_(r)-D where D is independently one or more higher diamondoid groupsand r is an integer from 1 to 1,000,000, and preferably from 1 to 1000.

For cationic polymerization, a cationic catalyst is used to promote thereaction. Suitable catalysts are typically Lewis acid catalysts, such asboron trifluoride or aluminum trichloride. These polymerizationreactions are usually conducted in solutions at low temperature (e.g.,−80 to −100° C.).

Subjecting the derivative to anionic polymerization typically involvesthe addition of a strong nucleophile. Such nucleophiles include, forexample, Grignard reagents and other organometallic compounds. Anionicpolymerization reactions are oftentimes facilitated through the removalof water and oxygen from the medium, as those substances tend toterminate the polymerization reaction.

Where the polymerizable moiety is a suitable nucleophile (e.g., alcohol,amine and thiol) or electrophile (e.g., activated carboxylic acidderivative and epoxide), polymerization typically occurs through apolycondensation reaction. Examples of higher diamondoid-containingpolymers that are formed using such a method include polyesters,polyamides, polyimides, polyaspartimides, polyamideimides, polyethersand so on, are formed where a higher diamondoid derivative issubstituted such that it contains at least two different groups that cancouple to one another (e.g., amine and carboxylic acid to form anamide). Heteropolymers, e.g. copolymers, in contrast, are formed wherethe higher diamondoid derivative is substituted such that it contains atleast two groups (e.g., two carboxylic acid groups) that can couple toother bifunctional monomer(s), a linker such as (e.g.,1,3-diaminopropane).

The following are examples of polycondensation reactions involvinghigher diamondoid derivatives with a suitable linker: reaction ofdiepoxy higher diamondoid derivatives in the presence of a suitable diol(e.g., diethylene glycol) under either basic or acid conditions to formpolyethers; reaction of bisphenolic higher diamondoid derivatives witharomatic dicarboxylic acids or activated dicarboxylic acids (e.g., acidchlorides) using pyridine as an HCl quencher at a relatively hightemperature to form polyesters; reaction of bisphenolic higherdiamondoid derivatives with activated aromatic dihalides (i.e.,nucleophilic aromatic substitution polymerization) inN,N-dimethylacetamide (DMAc) in the presence of potassium carbonateunder reflux to form poly(aryl ethers); reaction of bisphenolic higherdiamondoid derivatives and aromatic bisphenols in different molar ratioswith activated aromatic dihalides to form co-polymers; reaction ofdiamino higher diamondoid derivatives with aromatic dicarboxylic acidsin the presence of triphenyl phosphite and pyridine to form polyamides;reaction of diamino higher diamondoid derivatives with aromatictetracarboxylic dianhydrides in the presence of DMAc and an equimolarmixture of acetic anhydride and pyridine to form polyimides; reaction ofdiamino higher diamondoid derivatives with aromatic tetracarboxylicdianhydrides in m-cresol under reflux to form polyimides; reaction ofdiamino higher diamondoid derivatives withbis(3-ethyl-5-methyl-4-maleimidophenyl)methane in m-cresol in thepresence of glacial acetic acid to form linear polyaspartimides; and,reaction of dicarboxyl higher diamondoid derivatives with diamines ordialcohols under suitable polycondensation conditions to formpolyesters, polyamides or polyamide-imides.

As shown in FIGS. 4A-4H, the higher diamondoids can be incorporated intopolymers in a wide range of configurations. FIG. 4A shows a homopolymerin which the higher diamondoid is a recurring unit pendant from thepolymer backbone.

FIGS. 4B and 4C show copolymers or terpolymers where CP and CP2 are oneor more copolymeric units, and the diamondoid is again pendant. Whencopolymeric units are present, their proportion to the proportion ofhigher diamondoid, for instance the ratio of n to m in the polymer of 4Bor the ratio of n to m+p in the polymer of 4C can vary widely.Proportions (based on number of units) can range from 1 part higherdiamondoid/0-1000 parts copolymeric unit with ratios of 1 part higherdiamondoid/0-500 parts of copolymeric unit being preferred.

The higher diamondoid can also be incorporated into the backbone, perse. A representative homopolymer is shown in FIG. 4D and a copolymer isshown in FIG. 4E.

As shown in FIGS. 4F and 4G, a polymer can also have a preformedbackbone with the diamondoids pendant from it.

As shown in FIG. 4H, the higher diamondoid derivatives can function as across-linker, in which case the higher diamondoid links two polymerchains.

A range of polymerization reactions are depicted in FIG. 41 whereprepresentative higher diamondoid derivatives are shown together withreaction routes to polymers.

Higher Diamondoid-Containing Polymers

As just described, the polymers contain higher diamondoids as recurringunits. They may be present as part of the polymer backbone, assidegroups or as branches off of the chain.

In one embodiment, the polymer comprises multiple copies of the same ordifferent higher diamondoid covalently bonded to each other andpreferably attached through a linker. Such resulting polymer may be ahomopolymer or in another aspect, a co-polymer. Accordingly, one suchpolymer represented by formula(D)_(q)-Lwherein

-   -   D is a higher diamondoid;    -   L is a linker having at least two complementary functional        groups wherein at least one functional group is covalently        bonded to the higher diamondoid; and    -   q is an integer from 2 to 1000 or higher.

In yet another embodiment, the polymer comprises multiple copies of thesame or different higher diamondoid attached to multiple copies of thesame or different linker, these polymers also may be homopolymers orheteropolymers. Such a polymer is represented by formula:D-L(-D-L)_(r)-Dwherein

-   -   each D is independently a higher diamondoid group;    -   L is a linker; and    -   r is an integer from 1 to 1,000,000 and preferably from 1 to        1000.

In yet another aspect of this invention the higher diamond derivativescan be covalently bonded to each other through their derivatizingmoieties (R) without the use of a linker, accordingly such polymersformed can be represented by

where each D is independently selected from a higher diamondoid group, Ris a derivatizing group and n is an integer from 2 to 1000 or higher.

In another embodiment, the higher diamondoid derivative contains asingle polymerizable moiety and is formed into a dimeric material byreaction with a single linker. For example, a dimeric diamondoidstructure of the formula:

which could be prepared by reaction of a carboxyl containing higherdiamondoid derivative with ethylene diamine to provide e.g. [higherdiamondoid]-C(O)NHCH₂CH₂NHC(O)-[higher diamondoid]. In another aspect,there are multiple higher diamondoids attached to a common linker orbackbone.

The variety of polymers formed from the polymerizable higher diamondoidsderivatices is shown in FIG. 4 which illustrate representative types andclasses of polymers. In these formulae, D is a higher diamoindoidderivative and CP, etc. are copolymerizable materials.

Many of these polymers include a linking group which can react with twoor more diamondoid derivatives. Such linking moieties can for example,be derived from diacids, dicarboxcylic acids, disulfonyl halides,dialdehydes, diketones, dihalides, diisocyanates, diamines, diols,dithiols, and the like or mixtures of carboxylic acids, sulfonylhalides,aldehydes, ketones, diols and the like.

A preferred linker L, may be represented by the following formula:—X^(a)—Z^(a)(Y^(a)—Z^(a))_(m)—Y^(b)—Z^(a)—X^(a)—;in which m is an integer from 0 to 50, preferably from 0 to 20, X^(a) ateach separate occurrence is selected from the group consisting of —O—,—S—, —NR²⁰—, —C(O)—, —C(O)O—, —C(O)NR²⁰—, —C(S), —C(S)O—, —C(S)NR²⁰— ora covalent bond, wherein the R²⁰s, at each separate occurrence, areindependently defined as selected from the group consisting of hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl,substituted alkynyl, aryl, heteroaryl and heterocyclic; Z^(a) is at eachseparate occurrence is selected from the group consisting of alkylene,substituted alkylene, cycloalkylene, substituted cylcoalkylene,alkenylene, substituted alkenylene, alkynylene, substituted alkynylene,cycloalkenylene, substituted cycloalkenylene, arylene, heteroarylene,heterocyclene, or a covalent bond; Y^(a) and Y^(b) at each separateoccurrence are selected from the group consisting of —C(O)NR²¹—,—NR²¹C(O)—, —NR²¹C(O)NR²¹—, —C(═NR²¹)—NR²¹—, —NR²¹C(═NR²¹)—,—NR²¹—C(O)—O—, —N═C(X^(a))—NR²¹—, —P(O)(OR²¹)—O—, —S(O)_(n)CR²¹R²²—,—S(O)_(n)—NR²¹—, —S—S— and a covalent bond, where n is 0, 1, and 2; andwherein R²¹ and R²² at each separate occurrence are independentlydefined as selected from the group consisting of hydrogen, alkyl,substituted alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,substituted alkenyl, cycloalkenyl, substituted cycloalkenyl, alkynyl,substituted alkynyl, aryl, heteroaryl and heterocyclic; provided that atleast one of X^(a), Y^(a), Y^(b) or Z^(a) is not a covalent bond.

Some of the preferred linkers can be derived from mono or polyamide,mono or polyimide, mono or polyurethane, mono or polyacetal, mono orpolyethylene, mono or polyisobutenylene, mono or polyacrylonitril, monoor polycarbonate, mono or poly(vinyl chloride), mono or polystyrene,mono or polyvinyl acetal, mono or poly(methyl metharcylate), mono orpoly(vinylidene chloride), mono or polyisoprene, mono orpolyoxymethylene, mono or polyaspartimides, polyamideimides and thelike.

Exemplary diamondoid-containing polymers are illustrated schematicallyin FIGS. 5A-5C. Referring to FIG. 5A, a diamondoid-containing polymer isshown generally at 200, where the polymer comprises diamondoid monomers201, 202, 203 linked through carbon-to-carbon covalent bonds 204. Thediamondoid monomers 201, 202, 203 may comprise any member of the higherdiamondoid series tetramantane through undecamantane. The covalentlinkage 204 comprises a bond between two carbon atoms where each ofcarbon atoms of the bond are members of the two adjacent diamondoids.Stated another way, two diamondoids in the polymeric chain are directlylinked such that there are no intervening carbon atoms that are not partof a diamondoid nucleus (or part of an adamantane subunit).

Alternatively, two adjacent diamondoids may be covalently linked throughcarbon atoms that are not members (part of the carbon nucleus) of eitherof the two diamondoids. Such a covalent linkage is shown schematicallyin FIG. 5A at reference numeral 205. As discussed above, adjacentdiamondoids may be covalently connected through, for example, an esterlinkages 206, an amide linkages 207, and an ether linkage is 208.

In an alternative embodiment, a diamondoid-containing polymer showngenerally at 220 in FIG. 5B comprises a copolymer formed from themonomers ethylene and a higher diamondoid having at least one ethylenesubstituent. The diamondoid monomer shown at 221 contains onesubstituent ethylene group. The diamondoid monomer shown at 222 containstwo ethylene substituents, and could have more than two substituents.Either or both of these diamondoids may be copolymerized with ethylene223 itself, as a third monomer participating in the reaction, to formthe co-polymer 220 or subunits thereof. Because the diamondoid monomer222 has two substituent polymerizable moieties attached to it, thisparticular monomer is capable of cross-linking chains 224 and chain 225together. Such a cross-linking reaction is capable of producing polymershaving properties other than those of the polymer depicted in FIG. 5A,since for the FIG. 5A polymer the diamondoid nucleus are positionedwithin the main chain. A consequence of the structures formed in FIGS.5A and 5B is that it is possible to incorporate metallic elements,particles, and inclusions (illustrated as M1 to M3) by inserting theminto the interstities of folded and cross-linked polymeric chains. Therelative ratios of the monofunctional diamondoid monomer, thedifunctional diamondoid monomer, and the ethylene monomer in theexemplary polymer of FIG. 5B may of course be adjusted to produce thedesired properties with regard to stiffness, compactness, and ease ofprocessing.

The exemplary polyimide-diamondoid polymer shown generally at 230 inFIG. 5C contains segments of polyimide chains derived fromrepresentative groups selected to illustrate certain relationshipsbetween structure and properties, in particular, how the properties ofthe exemplary polymer relate to the processing it has undergone. Thedianhydride PMDA (pyromellitic dianhydride) shown at 231 and the diaminediaminofluorenone 232 are introduced into the chain for rigidity. Thedianhydride BTDA (benzophenonetetracarboxylic dianhydride) shown at 233provides the capability of further reaction at the carboxyl site,possibly for crosslinking purposes, and/or for the potential inclusionof metallic moieties into the material. The dianhydride oxydiphthalicdianhydride (ODPA) shown at 234, and the diamines oxydianiline (ODA) at235 and bisaminophenoxybenzene at 236 may be introduced for chainflexibility and ease of processing of the material. Additionally,fluorinated dianhydrides such as 6FDA (not shown) may be introduced tolower the overall dielectric constant of the material.

The diamondoid components of the exemplary polymer illustratedschematically in FIG. 5C comprise a pentamantane diamondoid at 236,which is positioned in the main chain of the polymer, and an octamantanediamondoid at 237, which comprises a side group of thediamondoid-polyimide polymer at a position of a diamine (in thisexemplary case, diaminobenzophenone) component. A diamondoid component238 may be used as a cross-linking agent to connect two adjacent chains,through covalent linkages, or diamondoid component 238 may be passivelypresent as an unfunctionalized “space filler” wherein it serves toseparate main polymeric chains simply by steric hindrance. Folding ofthe main polymeric chains, particularly when diamondoid “fillers” 238are present, may create voids 239, which may serve to reduce the overalldielectric constant of the material, since the dielectric constant ofair (if it is the gas within the void), is one.

As shown in FIG. 1B the diamond nanocrystallites (higher diamondoids)that may be incorporated into a diamondoid-containing material ingeneral, and into polymeric materials in particular, have a variety ofwell-defined molecular structures, and thus they may be attached to eachother, attached to a main polymer chain, used as cross-linking agents,etc., in a great variety of ways.

The molecular sites and the geometries of the attachments of a higherdiamondoid to another diamondoid, and to a polymer chain, will alsoaffect the properties of resulting materials. For example, theinterconnection of higher diamondoid units through tertiary“bridge-head” carbons, as illustrated in FIG. 5E, will result instronger, more rigid materials than those which result frominterconnection through secondary carbons, as in FIG. 5F. Furthermore,attachment through tertiary carbons that are themselves bonded to thehighest number of quaternary carbons in a higher diamondoid(nanocrystallite) will provide the strongest, most rigid materials, asin FIG. 5D.

There are other properties of higher diamondoids that may be exploitedto design new materials with desirable properties. Higher diamondoidsdisplay classical diamond crystal faces such as the (111), (110), and(100) planes. These higher diamondoids may be oriented in materials suchas polymers so that the resulting diamond nanocrystallites may haveco-planer diamond faces. The diamondoids with chiral sturcture, may beused to fabricate the exemplary chiral polymers illustrated in FIGS.5G-5H. The kinds of chiral polymers have potential uses in photonics,and for the integration of photonic and electronic devices.

Utility

The polymers of the present invention can take a variety of forms andcan find a variety of applications. Such materials include compositematrix resins, structural adhesives and surface films that are used foraerospace structural applications. Furthermore, coating layers ormoldings with excellent optical, electrical or electronic and mechanicalproperties are produced for use in optical fibers, photoresistcompositions, conducting materials, paint compositions and printinginks.

In addition, higher diamondoid-containing polymers will have highthermal stability making them suitable for use in environments requiringsuch stability including for example, devices such as semiconductors,coatings for refractory troughs or other high temperature applications.Higher diamondoid containing polymers will also have improved wearresistance coatings which can could mean improved protection andextended lifetimes for metal or plastic tools, autoparts etc.

EXAMPLES

As used herein and in the Figures, the following abbreviations have thefollowing meanings. Any abbreviation not defined below has its generallyaccepted meaning.

API = American Petroleum Institute atm eqv = atmospheric equivalent btms= bottoms DMAc = N,N-dimethylacetamide NMP = N-methyl-2-pyrrolidone DMSO= dimethylsulfoxide DMF = dimethylformamide EOR Traps = end of run trapsfid = flame ionization detector g = grams GC = gas chromatography GC/MS= gas chromatography/mass spectroscopy h = hour HPLC = high performanceliquid chromatography HYD RDG = hydrometer reading L = liter min =minute mL = milliliters mmol = millimols N = normal pA = pico amps PEG =polyethylene glycol ppb = parts per billion ppm = parts per million RI =refractive index SIM DIS = simulated distillation ST = start TIC = totalion current TLC = thin layer chromatography THF = tetrahydrofuran UV =ultraviolet VLT = vapor line temperature VOL PCT = volume percent v/v =volume to volume wt = weight WT PCT = weight percentIntroduction

The steps used in the various Examples are shown schematically in FIG.7.

Example 1 describes a most universal route for isolating higherdiamondoids components which can be applied to all feedstocks. Thisprocess uses HPLC (Step 7, FIG. 7) as its final isolation step.

Example 2 describes a variation of the process of Example 1 in whichpreparative gas chromatography (Step 7′, FIG. 7) replaces HPLC as thefinal isolation step.

Example 3 describes a variation of the process of Example 1 in which thepyrolysis (Step 5, FIG. 7) is omitted. As shown optionally in FIG. 7,the liquid chromatographic step (Step 6, FIG. 7) is also omitted. Thesevariations generally have applicability only with selected feedstocksand generally when tetramantanes, pentamantane and cyclohexamantane arethe target higher diamondoids.

Example 4 describes yet another process variation in which the finalproducts of Examples 1 and 3 are subjected to preparative gaschromatography purification to give further separation of higherdiamondoid components (Step 8, FIG. 7).

Example 5 describes the Bromination of a mixedtetramantane-alkyltetramantane feed and shows the preparation of avariety of mono- and polybromonated tetramantane derivatives andintermediates.

Examples 6-45 describe methods that could be used to prepare higherdiamondoid derivatives and intermediates.

Examples 46-61 describe methods that could be used to prepare higherdiamondoid-containing polymers.

Examples 62-72 describe methods that could be used to prepare higherdiamondoid derivatives and intermediates.

Examples 73-79 describes additional methods that could be used toprepare higher diamondoid-containing polymers.

It will be understood that it is possible to vary the order of thevarious distillation, chromatography and pyrolysis steps, although theorder set forth in Example 1 has given the best results.

Example 1

This Example has seven steps (see Flow Chart in FIG. 7).

Step 1. Feedstock selection

Step 2. GCMC assay development

Step 3. Feedstock atmospheric distillation

Step 4. Vacuum fractionation of atmospheric distillation residue

Step 5. Pyrolysis of isolated fractions

Step 6. Removal of aromatic and polar nondiamondoid components

Step 7. Multi-column HPLC isolation of higher diamondoids

-   -   a) First column of first selectivity to provide fractions        enriched in specific higher diamondoids.    -   b) Second column of different selectivity to provide isolated        higher diamondoids.

This example is written in terms of isolating several hexamantanes.

Step 1—Feedstock Selection

Suitable starting materials were obtained. These materials included agas condensate, Feedstock A (FIG. 6), and a gas condensate containingpetroleum components, Feedstock B. Although other condensates,petroleums, or refinery cuts and products could have been used, thesetwo materials were chosen due to their high diamondoid concentration,approximately 0.3 weight percent higher diamondoids, as determined by GCand GC/MS. Both feedstocks were light colored and had API gravitiesbetween 19 and 20° API.

Step 2—GC/MS Assay Development

Feedstock A was analyzed using gas chromatography/mass spectrometry toconfirm the presence of target higher diamondoids and to provide gaschromatographic retention times for these target materials. Thisinformation is used to track individual target higher diamondoidsthrough subsequent isolation procedures. FIG. 8A is a table that liststypical GC/MS assay information for the hexamantanes (GC retentiontimes, mass spectral molecular ion (M+) and base peak). This table (FIG.8A) also contains similar GC/MS assay information for other higherdiamondoids. While relative G(retention times are approximatelyconstant, non-referenced GC retentions vary with time. It is recommendedthat GC/MS assay values be routinely updated especially when GCretention time drift is detected.

Step 3—Feedstock Atmospheric Distillation

A sample of Feedstock B was distilled into a number of fractions basedon boiling points to separate the lower boiling point components(nondiamondoids and lower diamondoids) and for further concentration andenrichment of particular higher diamondoids in various fractions. Theyields of atmospheric distillate fractions of two separate samples ofFeedstock B are shown in Table 3, below and are contrasted to simulateddistillation yields. As seen from Table 3, the simulated distillationdata is in agreement with the actual distillation data. The simulateddistillation data were used to plan subsequent distillation processes.

TABLE 3 Yields of Atmospheric Distillation Fractions from Two SeparateRuns of Feedstock B Sim Dis Feedstock B (Run 2) Cut (° F.) Est.'d Yields(Wt %) Yields (Wt %) Difference To 349 8.0 7.6 0.4 349 to 491 57.0 57.7−0.7 491 to 643 31.0 30.6 0.4 643 and higher 4.0 4.1 −0.1 Sim DisFeedstock B (Run 1) Cut (° F.) Est.'d Yields (Wt %) Yields (Wt %)Difference To 477 63.2 59.3 3.9 477 to 515 4.8 7.3 −2.5 515 to 649 28.531.2 −2.7 649 and higher 3.5 2.1 1.4Step 4—Fractionation of Atmospheric Distillation Residue by VacuumDistillation

The resulting Feedstock B atmospheric residium from Step 3 (comprising2-4 weight percent of the original feedstock) was distilled intofractions containing higher diamondoids as shown in FIGS. 9 and 10). Thefeed to this high temperature distillation process was the atmospheric650° F.+bottoms. Complete Feedstock B distillation reports are given inTables 4A and 4B. Tables 5A and 5B illustrate the distillation reportsfor Feedstock B 650° F.+distillation bottoms.

TABLE 4A Distillation Report for Feedstock B Feedstock B Column Used:Clean 9″ × 1.4″ Protruded Packed VAPOR DISTILLATION RECORD NORMALIZEDACTUAL TEMP WEIGHT VOLUME API DENSITY WT VOL WT VOL CUT ST - END G ml @60° F. 60/60 @ 60° F. PCT PCT PCT PCT 1 226 − 349 67.0 80 38.0 0.83487.61 8.54 7.39 8.26 2 349 − 491 507.7 554 22.8 0.9170 57.65 59.12 55.9857.23 3 491 − 643 269.6 268 9.1 1.0064 30.62 28.60 29.73 27.69 COLHOLDUP 0.2 0 6.6 1.0246 0.02 0.00 0.02 0.00 BTMS 643 + 36.1 35 6.61.0246 4.09 3.74 3.98 3.62 EOR TRAPS 0.0 0 0.00 0.00 0.00 TOTALS 880.6937 100.00 100.00 97.09 96.80 LOSS 26.4 31 2.91 3.20 FEED 907.0 968 19.50.9371 100.00 100.00 BACK CALCULATED API AND DENSITY 19.1 0.9396

TABLE 4B Distillation Report for Feedstock B Feedstock B Column Used:Clean 9″ × 1.4″ Protruded Packed TEMPERATURE DEGREES F. API GRAVITIESVAPOR OBSERVED ATM PRESSURE REFLUX CUT VOLUME WEIGHT HYD TEMP VLT EQV.POT TORR RATIO NO ml @ 60° F. G RDG ° F. 60° F. 93 225.8 262 50.000 3:1START OVERHEAD 198 349.1 277 50.000 3:1 1 80 67.0 39.6 80.0 38.0 321490.8 376 50.000 3:1 2 554 507.7 24.1 80.0 22.8 Cut 2 looks Milky, Whitecrystals form in Run Down Line. Heat Lamp applied to drip tube. Cool totransfer btms to smaller flask. 208 437.7 323 10.000 3:1 START OVERHEAD378 643.3 550 10.000 3:1 3 268 269.6 9.9 75.0 9.1 Shutdown due to drypot END OF RUN TRAPS 0 0.0 VOLUME DISTILLED 902 COLUMN HOLDUP 0 0.2 0.00.0 6.6 BOTTOMS 35 36.1 7.2 72.0 6.6 RECOVERED 937 880.6 FEED CHARGED968 907.0 20.7 80.0 19.5 LOSS 31 26.4

TABLE 5A Vacuum Distillation Report for Feedstock B Feedstock B -Atmospheric distillation resid 650° F. + bottoms Column Used: Sarnia HiVac TEMPERATURE DEGREES F. API GRAVITIES VAPOR OBSERVED ATM PRESSUREREFLUX CUT VOLUME WEIGHT HYD TEMP VLT EQV. POT TORR RATIO NO ml 60° F. GRDG ° F. 60° F. 315 601.4 350 5.000 START OVERHEAD 344 636.8 382 5.000300 READING 342 644.9 389 4.000 500 READING 344 656.3 395 3.300 1 639666.4 7.8 138.0 4.1 353 680.1 411 2.500 400 READING 364 701.6 430 2.1002 646 666.9 9.4 138.0 5.6 333 736.0 419 0.400 200 READING 336 751.9 4320.300 3 330 334.3 12.4 139.0 8.3 391 799.9 468 0.500 4 173 167.7 19.0139.0 14.5 411 851.6 500 0.270 5 181 167.3 26.8 139.0 21.7 460 899.8 5380.360 6 181 167.1 27.0 139.0 21.9 484 950.3 569 0.222 7 257 238.4 26.2139.0 21.2 Shut down distillation to check pot temperature limits withcustomer. (Drained trap material 5.3 grams) 472 935.7 576 0.222 521976.3 595 0.340 8 91 85.4 23.7 139.0 18.9 527 999.9 610 0.235 9 85 80.823.0 139.0 18.2 527 1025.6 624 0.130 10 98 93.8 21.6 139.0 16.9 Drainedremaining trap material of 16.5 grams (~4 grams of water) MID END OF RUNTRAPS 20 17.8 (mathematically AND combined) VOLUME DISTILLED 2701 COLUMNHOLDUP 4 4.0 0.0 0.0 3.4 BOTTOMS 593 621.8 11.0 214.0 3.4 RECOVERED 32983311.7 FEED CHARGED 3298 3326.3 18.0 234.0 8.6 LOSS −5 14.6

TABLE 5B Distillation Report for Feedstock B-btms Feedstock B -Atmospheric distillation resid 650° F. + bottoms Column Used: SarniaHiVac VAPOR TEMP WEIGHT VOLUME API DENSITY WT VOL WT VOL CUT ST - END Gml @ 60° F. 60/60 60° F. PCT PCT PCT PCT 1 601 − 656 666.4 639 4.11.0435 20.12 19.38 20.03 19.40 2 656 − 702 666.9 646 5.6 1.0321 20.1419.59 20.05 19.62 3 702 − 752 334.3 330 8.3 1.0122 10.09 10.01 10.0510.02 4 752 − 800 167.7 173 14.5 0.9692 5.06 5.25 5.04 5.25 5 800 − 852167.3 181 21.7 0.9236 5.05 5.49 5.03 5.50 6 852 − 900 167.1 181 21.90.9224 5.05 5.49 5.02 5.50 7 900 − 950 238.4 257 21.2 0.9267 7.25 7.797.17 7.80 8 950 − 976 85.4 91 18.9 0.9408 2.58 2.76 2.57 2.76 9 976 −1000 80.8 85 18.2 0.9452 2.44 2.58 2.43 2.58 10 1000 − 1026 93.8 98 16.90.9535 2.83 2.97 2.82 2.98 COL HOLDUP 4.0 4 3.4 1.0489 0.12 0.12 0.120.12 BTMS 1026 + 621.8 593 3.4 1.0489 18.78 17.98 18.69 18.01 EOR TRAPS17.8 20 0.54 0.61 0.54 0.61 TOTALS 3311.7 3298 100.00 100.00 99.56100.15 LOSS 14.6 −5 0.44 −0.15 FEED 3326.3 3293 8.6 1.0100 100.00 100.00BACK CALCULATED API & DENSITY 9.4 1.0039

TABLE 6 Elemental Composition of Feedstock B Analyses on Feedstock B650 + F Resid Measured Value Nitrogen 0.991 wt % Sulfur 0.863 wt %Nickel 8.61 ppm Vanadium <0.2 ppm

Table 6 illustrates the partial elemental composition of Feedstock Batmospheric distillation (650° F.) residue including some of theidentified impurities. Table 6 displays the weight percent nitrogen,sulfur, nickel and vanadium in Feedstock B atmospheric distillationresidue. Subsequent steps remove these materials.

Step 5—Pyrolysis of Isolated Fractions

A high-temperature reactor was used to pyrolyze and degrade a portion ofthe nondiamondoid components in various distillation fractions obtainedin Step 4 (FIG. 7) thereby enriching the diamondoids in the residue. Thepyrolysis process was conducted at 450° C. for 19.5 hours. The gaschromatogram (FID) of fraction #6 (Table 5B) is shown in FIG. 11A. FIG.11B is the chromatogram for the product of pyrolysis. A comparison ofthese chromatograms shows that pyrolysis has removed major nondiamondoidhydrocarbons and has significantly increased the higher diamondoidconcentration, especially the hexamantanes. A 500 mL PARR® reactor fromPARR Instrument Company, Moline, Ill. was used in this pyrolysis step.

Step 6—Removal of Aromatic and Polar Nondiamondoid Components

The pyrolysate produced in Step 5 was passed through a silica-gelgravity chromatography column (using cyclohexane elution solvent) toremove polar compounds and asphaltenes (Step 6, FIG. 7). The use of asilver nitrate impregnated silica gel (10 weight percent AgNO₃) providescleaner diamondoid-containing fractions by removing the free aromaticand polar components. While it is not necessary to use thischromatographic aromatic separation method, it facilitates subsequentsteps.

Step 7—Multi-Column HPLC Isolation of Higher Diamondoids

An excellent method for isolating high-purity higher diamondoids usestwo or more HPLC columns of different selectivities in succession.

The first HPLC system consisted of two Whatman M20 10/50 ODS columnsoperated in series using acetone as mobile phase at 5.00 mL/min. Aseries of HPLC fractions were taken (see FIG. 12A). Fractions 36 and 37were combined and taken for further purification on a second HPLCsystem. This combined fraction (36 and 37) contained hexamantanes #7,#11 and #13. (FIG. 12A).

Further purification of this combined ODS HPLC fraction was achievedusing a Hypercarb stationary phase HPLC column having a differentselectivity in the separation of various hexamantanes than the ODScolumn discussed above. FIG. 12B shows elution times of the individualhexamantanes on the Hypercarb HPLC column (with acetone as a mobilephase).

The differences in elution times and elution order of hexamantanes onODS and Hypercarb HPLC columns are seen by comparing these two FIGS. 12Aand 12B. For example, Hexamantanes #11 and #13 elute together on the ODSHPLC system (FIG. 12A) but in separate fractions (fractions 32 and 27,respectively) on the Hypercarb system (FIG. 12B).

The different elution orders and times of selected higher diamondoids onthese two systems can be used to separate co-eluting higher diamondoids.It can also be used to remove impurities. Using this method on combinedODS HPLC fractions 36 & 37, appropriate Hypercarb HPLC fractions weretaken thus providing high-purity hexamantane #13 (FIGS. 13A and 13B).Other ODS HPLC fractions and Hypercarb HPLC cut points could be used toisolate the remaining hexamantanes. This isolation strategy is alsoapplicable to the other higher diamondoids although elution solventcompositions can vary.

The ODS and Hypercarb columns can also be used in reverse order forthese isolations. By using similar methodology as above, i.e.fractionating hexamantane-containing ODS fractions using the Hypercarbor other suitable column and collecting at corresponding elution timescan lead to the isolation of the remaining hexamantanes in high purity.This is also true of the other higher diamondoids from tetramantanes toundecamantanes, including substituted forms.

Example 2

Steps 1, 2, 3, 4, 5 and 6 of Example 1 were repeated (FIG. 7). Thefollowing variation of Step 7 was then carried out.

Step 7′:

A two-column preparative capillary gas chromatograph was used to isolatehexamantanes from the product of Example 1, Step 6. The cut times forthe hexamantanes were set for the first preparative capillary the GCcolumn, methyl silicone DB-1 equivalent, using the retention times andpatterns from GC/MS assay (Example 1, Step 2). The results are shown inFIG. 14A, two cuts identified as “peaks cut and sent to column 2”, weretaken which contains two of the hexamantane components from Feedstock B.The preparative capillary gas chromatograph used was manufactured byGerstel, Inc., Baltimore, Md., USA.

The first column was used to concentrate the higher diamondoids, such ashexamantanes by taking cuts that were then sent to the second column(see FIG. 14B illustrated for hexamantane #2 and #8). The second column,phenyl-methyl silicone, a DB-17 equivalent, further separated andpurified the hexamantanes and then was used to isolate peaks of interestand retain them in individual traps (traps 1-6). GC trap fraction 1contained crystals of hexamantane #2. GC trap fraction 3 containedcrystals of hexamantane #8. Subsequent GC/MS analysis of trap #1material (FIGS. 15A and 15B) showed it to be high purity hexamantane #2based upon the GC/MS assay of Step 2. Similarly, the GC analysis of trap#3 material (FIGS. 15B and 15D) showed it to be primarily hexamantane#8. Photomicrographs of hexamantane #2 and #8 crystals. This procedurecould be repeated to isolate the other hexamantanes. This is also trueof the other higher diamondoids.

Example 3

Steps 1, 2, 3, and 4 (FIG. 7) of Example 1 were repeated using FeedstockA. Feedstock A is especially low in nondiamondoids in the atmosphericresidue fraction recovered in Step 4. The pyrolysis Step (5) of Example1 may be omitted especially when the higher diamondoids being sought aretetramantanes, pentamantanes and cyclohexamantane. In this case thefractions removed in Step 4 go directly to Steps 6 and 7 in Example 1 ordirectly to Step 7 in Example 2 (FIG. 7). This process variation can beapplied to lower-boiling tetramantane-containing fractions of FeedstockB as well. However, pyrolysis is highly desirable where significantnondiamondoid components are present.

A fraction corresponding in cut point to fraction #1 of Step 4 (seedistillation Table 3, Example 1 and FIG. 8) was taken from thisfeedstock. This fraction was further fractionated by preparativecapillary gas chromatography similar to the processing shown in Step 7′of Example 2 (FIG. 7).

A two-column preparative capillary gas chromatograph was then used toisolate the target tetramantanes from the distillate fraction cleaned-upby column chromatography (Step 6, FIG. 7). Using the retention times andpatterns from the GC/MS assay (from Step 2 of Example 1), the cut timesfor the target diamondoids (e.g., tetramantanes) were set for the firstpreparative capillary GC column, methyl silicone DB-1 equivalent. Theresults are shown on the top of FIG. 16 identified as cuts 1, 2 and 3.

The first column was used to concentrate the target diamondoids (e.g.,tetramantanes) by taking cuts that were then sent to the second column(phenylmethyl silicone, a DB-17 equivalent) (see the bottom of FIG. 16).The second column further separated and purified the target diamondoidsand then sent them into individual traps (traps 1-6). GC traps 2, 4 and6 contained the selected tetramantanes (FIG. 16).

The highly concentrated tetramantane higher diamondoids were thenallowed to crystallize in the trap or dissolved and recrystallized fromsolution. Under the microscope at 30× magnification, crystals of thetetramantanes were visible in preparative GC traps 2, 4, and 6. Whereconcentrations were not high enough for crystallization to occur,further concentration by preparative GC was necessary. The process wouldalso work to isolate other higher diamondoids from Feedstock A.

Example 4 Preparative GC of HPLC Fractions

With the heptamantanes, octamantanes and higher diamondoids, etc., itmay be desirable to further fractionate the HPLC products obtained inExample 1, Step 7. This can be carried out using preparative capillarygas chromatography as described in Example 2, Step 7′.

The following higher diamondoid components were isolated andcrystallized: all of the tetramantanes from both Feedstocks A and B, allpentamantanes (mol. wt. 344) isolated from Feedstock B; two hexamantanecrystals (mol. wt. 396) isolated from Feedstock B; and, two heptamantanecrystals (mol. wt. 394) isolated from Feedstock B, octamantane crystal(mol. wt 446) isolated from Feedstock B. As well as a nonamantanecrystal (mol. wt. 498) and a decamantane crystal (mol. wt. 456) isolatedfrom Feedstock B. The other higher diamondoid components could also beisolated using the procedures set forth in these examples.

Example 5 Bromination of Higher Diamondoid Containing Feedstock

Bromination of a feedstock containing a mixture of higher diamondoidswas carried out.

The feedstock was derived from Feedstock B described in Example 1. Asample of Feedstock B was subjected to atmospheric distillation as setforth in Example 1, Step 3. At the completion of the distillation aholdup fraction was obtained by rinsing the column. Its composition wassimilar to that of vacuum distillation fraction 1 indicated in FIG. 9.The holdup fraction was fractionated on a Whatman M40 10/50 ODSpreparative scale HPLC column using acetone as mobile phase.

A fraction containing all of the tetramantanes including somealkyltetramantanes and hydrocarbon impurities was obtained. Thecomposition of this fraction is shown in FIG. 17. The tetramantanes wereidentified by mass spectra and retention times.

This fraction (about 10 mg) was mixed with anhydrous bromine excess(dried with concentrated H₂SO₄) in a 10 mL round-bottom flask. Whilestirring, the mixture was heated in an oil bath for about 4.5 hoursunder nitrogen, whereby the temperature was gradually raised from roomtemperature to about 100° C. The excess bromine was then removed byevaporation and the resulting brownish product was characterized byGC/MS.

FIG. 18 shows the monobrominated, dibrominated and tribrominatedtetramantane products formed (characterized by molecular ion 371, 447and 527 respectively).

FIG. 19 shows the presence of monobrominated tetramantanes in the totalion chromatogram of the reaction product showing that these compoundsare the major components within this GC/MS retention time range.

FIG. 20 shows the presence of di- and tri-brominated tetramantaneproducts in the reaction mixture as the major components within thisGC/MS retention time range.

FIG. 21 shows the presence of a monobrominated tetramantane in the totalion chromatogram of the reaction mixture.

FIG. 22 is the mass spectrum of a monobrominated tetramantane with GC/MSretention time of 12.038 minutes from (FIG. 21). The base peak in thisspectrum is the 371 m/z molecular ion.

FIG. 23 shows the presence of monobrominated methyltetramantanes in thetotal ion chromatogram of the reaction product.

FIG. 24 are the mass spectra of monobrominated methyltetramantanes fromFIG. 23 with GC/MS retention times of 11.992 minutes and 11.644 minutes.The base peak in this spectrum is the 385 m/z molecular ion.

FIG. 25 shows the presence of brominated dimethyltetramantane in thetotal ion chromatogram of the product.

FIG. 26 is the mass spectrum of the monobrominated dimethyltatramantaneeluting at 12.192 minutes from FIG. 25.

FIG. 27 shows the presence of dibrominated tetramantane in the total ionchromatogram of the reaction product.

FIG. 28 is the mass spectrum of a dibrominated tetramantane with GC/MSretention time of 15.753 minutes from FIG. 27. The base peak in thisspectrum is the 447 m/z molecular ion.

FIG. 29 shows the presence of dibrominated methyltetramantane in thetotal ion chromatogram of the reaction product.

FIG. 30 is the mass spectrum of a dibrominated methyltetramantane withGC/MS retention time of 15.879 minutes from FIG. 30. The base peak inthis spectrum is the 461 m/z molecular ion.

FIG. 31 shows the presence of tribrominated tetramantane in the totalion chromatogram of the reaction product.

FIG. 32 is the mass spectrum of a tribrominated tetramantane with GC/MSretention time of 17.279 minutes from FIG. 31. The base peak in thisspectrum is the 527 m/z molecular ion.

FIG. 33 shows the presence of tribrominated methyltetramantane in thetotal ion chromatogram of the reaction product.

FIG. 34 is the mass spectrum of a tribrominated methyltetramantane withGC/MS retention time of 15.250 minutes from FIG. 34. The molecular ionis 541 m/z.

Example 6 Monobromination of Higher Diamondoids

A higher diamondoid (7.4 mmol) is mixed with anhydrous bromine (74 mmol)in a 150 mL round bottom flask. While stirring, the mixture is heated inan oil bath for about 4.5 h, whereby the temperature is gradually raisedfrom an initial 30° C. to 105° C. The product monobrominated higherdiamondoid dissolved in excess bromine is cooled and then taken up with100 mL carbon tetrachloride which is poured into 300 mL ice water. Theexcess bromine is removed with sodium hydrogen sulfide while continuingcooling with ice water. After the organic phase has been separated, theaqueous solution is extracted once more with carbon tetrachloride. Thecombined extracts are washed with water, three times. After the organicphase has been dried with calcium chloride, the solvent is distilled offand the last residues are removed under vacuum. The residue is dissolvedin a small amount of methanol and crystallized in a cold bath. Furtherpurification of the crystals is carried out by sublimation under vacuum.

Example 7 Dibromination of Higher Diamondoids without Catalysts

A higher diamondoid (37 mmol) is heated to 150° C. for about 22 h withanhydrous bromine (0.37 mol) in a pressure vessel. The typical work-upand recrystallization of the oily reaction product from methanol isperformed as described above. The crystals are sublimated in vacuum. Thesublimate is recrystallized several times from a very small amount ofn-hexane affording a pure dibrominated derivative.

Example 8 Dibromination of Higher Diamondoids with Catalysts

To a stirred mixture of 1.0 mol anhydrous bromine and 0.025 mole (2.5mL) of boron bromide is added a few milligrams of aluminum bromide. Thereaction mixture is maintained under a blanket of nitrogen duringaddition of reactants to a four-necked flask with stirrer, refluxcondenser, and gas inlet. A higher diamondoid (0.1 mole) is addedportionwise from a small flask attached to the fourth neck by means ofGooch crucible tubing. After refluxing for about 1.5 hours, hydrogenbromide evolution is no longer evident. Excess bromine is decomposed andthe product isolation is accomplished as described above. After removalof the solvent, the residue is recrystallized frum methanol and n-hexaneat room temperature to provide a pure dibrominated compound.

Example 9 Brominated Higher Diamondoids from Hydroxylated Compounds

A mixture of a suitable hydroxylated higher diamondoid and excess 48%hydrobromic acid is heated to reflux for a few hours (which can beconveniently monitored by GC analysis), cooled, and extracted with ethylether. The extract is combined and washed with aqueous 5% sodiumhydroxide and water, and dried. Evaporation and normal columnchromatography on alumina eluting with light petroleum ether, hexane, orcyclohexane, or their mixtures, with ethyl ether affords the bromidewith reasonably high yields.

Example 10 Monophotochlorination of Higher Diamondoids

Photochlorination of a higher diamondoid is carried out at roomtemperature (25-30° C.) by metering 0.037 mole of chlorine into asolution of 0.074 mole of a higher diamondoid in 100 mL of solvent inthe presence of illumination by a 150-watt ultraviolet (UV) lamp. Thesolvents employed can be carbon tetrachloride, benzene, or carbondisulfide. After a short induction period (approximately 2 minutes) thereaction may be initiated as evidenced by the fading of the chlorinecolor and the evolution of hydrogen chloride. The reaction mixture iswashed by 5% sodium carbonate aqueous solution, water, and dried overanhydrous sodium sulfate. The product obtained by concentration of thedried solution is shown by GC to consist of several mono-chlorinatedhigher diamondoid isomers. Separation of those isomers is achieved byHPLC or even normal column chromatography on alumina, or silica gel, orsimply by recrystallization from methanol and sublimation under vacuum,or by a combination of separation techniques as described herein toachieve the isomer separation.

Example 11 Monochlorination of Higher Diamondoids

A solution of 0.074 mole of a higher diamondoid and 10 mL (8.5 g, 0.092mole) of tert-butyl chloride in 40 mL of anhydrous cyclohexane isprepared in a 0.1 L, three-necked, round-bottom flask fitted with athermometer, a stirrer, and a gas exhaust tube leading to a bubblersubmerged in water. The catalyst, aluminum chloride (total 0.46 g, 0.006mole), is added in batches of 0.05g at regular intervals over a periodof about 8 hours. Progress of the reaction is followed conveniently bythe rate of escaping isobutane gas. Upon completion of the reaction, 10mL of 1.0 N hydrochloride acid solution is added with vigorous stirring,followed by 50 mL of ethyl ether. The organic layer is separated, washedwith 10 mL of cold water and 10 mL of a 5% sodium bicarbonate solution,and dried over anhydrous calcium chloride. After removal of the solventsunder reduced pressure, the crude product is obtained. A GC analysis ofthis material reveals a composition of mainly monochlorinated higherdiamondoids with a small amount of unreacted higher diamondoid. Ifnecessary, recrystallization of a sample of this material from ethanolat −50° C. affords a pure monochlorinated higher diamondoid.

Example 12 Monohydroxylation of Higher Diamondoids

A solution of 11.0 mmol of a higher diamondoid in 18.7 g of methylenechloride is mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) ofperacetic acid in ethyl acetate. While being stirred vigorously, thesolution is irradiated with a 100-watt UV light placed in an immersionwell in the center of the solution. Gas evolution is evident from thestart. The temperature is maintained at 40-45° C. for an about 21-hourirradiation period. At the end of this time, about 95% of the peraceticacid had been consumed. The solution is concentrated to near dryness,treated twice in succession with 100-mL portions of toluene andreevaporated to dryness. Final drying in a desiccator affords a whitesolid. A portion of the above material is dissolved in a minimum amountof benzene-light petroleum ether. This solution is then subjected tochromatography on alumina in the usual manner eluting with firstly 1:1benzene/light petroleum ether, followed by a mixture of methanol andethyl ether, to collect the unreacted higher diamondoid and thehydroxylated higher diamondoid isomers, respectively. Further separationof the isomers can be achieved by using HPLC techniques.

Alternatively, to 25 mL of acetic acid are added 10 mmol of a higherdiamondoid, 0.8 mmol of N-hydroxyphthalimide (NHPI) and 0.6 mmol ofacetylacetonatocobalt(II). The resultant mixture is stirred in an oxygenatmosphere at a temperature of 75° C. for about 3 hours. The reaction ismonitored by GC, allowing for the isolation of the monohydroxylatedhigher diamondoid upon completion.

Example 13 Monohydroxylated Higher Diamondoids from MonobrominatedCompounds

A suitable monobrominated higher diamondoid (0.066 mol) is heated toreflux for about 1 h in a round bottom flask. This flask is equippedwith a stirrer and a reflux condenser to which 35 mL water, 3.5 mLtetrahydrofuran, 2.0 g potassium carbonate and 1.3 g silver nitrate isadded while stirring the mixture. After cooling, the reaction producthas crystallized, is separated and extracted with tetrahydrofuran. Theextract is diluted with water and the precipitate is suctioned off,dried and purified by sublimation under vacuum.

Alternatively, a suitable monobromo higher diamondoid (0.1 mole) ismixed with 40 mL of 0.67 N hydrochloric acid and 450 mL DMF. Theresultant mixture is stirred at reflux temperature for about 1 hour. Thesolid product is filtered and recrystallized from n-hexane to producethe monohydroxylated higher diamondoid.

Example 14 Dihydroxylated Higher Diamondoids from Dibrominated Compounds

A suitable dibrominated higher diamondoid (0.066 mol) is heated,refluxing for about 1 h in a round bottom flask. The flask is equippedwith a stirrer and a reflux condenser. While stirring, the following isadded: 70 mL water, 10 mL tetrahydrofuran, 4.0 g potassium carbonate and2.6 g silver nitrate. After cooling, the reaction product is separatedout and extracted with tetrahydrofuran. The extract is diluted withwater and the precipitate is suctioned off, dried and purified bysublimation under vacuum.

Alternatively, a mixture of a dibromo higher diamondoid (0.12 mole) and70% nitric acid (200 mL) is heated at 70-75° C. until bromine evolutionceases. The reaction mixture is poured into water (250 mL) and theprecipitate is filtered. The filtrate is made alkaline with 10% aqueoussodium hydroxide and the mixture is filtered. The combined precipitatesare washed with water (3×200 mL) and acetone (2×150 mL) and dried toprovide the desired compound.

Example 15 Polyhydroxylation of Higher Diamondoids

Into a 4-neck flask immersed in a cooling bath equipped with thefollowing: a low temperature condenser (−20° C.), an air drivenwell-sealed mechanical stirrer, a solid addition funnel and athermocouple. To this flask the following is added: 0.037 mole of ahigher diamondoid, 150 mL methylene chloride, 200 mL double distilledwater, 192 grams sodium bicarbonate and 300 mL t-butanol. This mixtureis stirred and cooled to 0° C. and 200 grams 1,1,1-trifluoro-2-propanone(TFP) is added. The mixture is stirred and cooled down to −8° C. Then,200 grams oxone is added from the solid addition funnel over the courseof 3 hours. The reaction mixture is stirred at 0° C. approximatelyovernight (16 hours). The TFP is recovered by distillation (heating potto 40° C. and condensing TFP in a receiver immersed in dry ice/acetone).The remainder of the mixture is filtered by suction and a clear solutionis obtained. The solution is rotavapped to dryness, providing a mixtureof polyhydroxylated higher diamondoids that can be purified bychromatography and/or recrystallization.

Example 16 Oxidation of Higher Diamondoids to Higher Diamondoidones

A solution of 11.0 mmol of a suitable higher diamondoid in 18.7 g ofmethylene chloride is mixed with 4.22 g of a solution of 1.03 g (13.5mmol) of peracetic acid in ethyl acetate. While being stirredvigorously, the solution is irradiated with a 100-watt UV light placedin an immersion well in the center of the solution. Gas evolution isevident from the start. The temperature is maintained at 40-45° C. foran about 21-hour irradiation period. At the end of this time, about 95%of the peracetic acid is consumed. The solution is concentrated to neardryness, treated twice in succession with 100-mL portions of toluene andis reevaporated to dryness. Final drying in a desiccator affords asolid.

The solid, a hydroxylated higher diamondoid mixture, is then partiallydissolved in acetone. The oxygenated components of this mixture go intothe solution but not all of the unreacted higher diamondoid. Chromicacid-sulfuric acid solution is added dropwise until an excess ispresent, and the reaction mixture is stirred overnight. The acetonesolution is decanted from the precipitated chromic sulfate and theunreacted higher diamondoid, and is dried with sodium sulfate. Theunreacted higher diamondoid is recovered by dissolving the chromiumsalts in water and filtering. Evaporation of the acetone solutionaffords a white solid. This crude solid is chromatographed on aluminawith standard procedures eluting first with 1:1 (v/v) benzene/lightpetroleum ether, followed by ethyl ether, or a mixture of ethyl etherand methanol (95:5 v/v), to collect the unreacted higher diamondoid andthe higher diamondoidone, respectively. Further purification byrecrystallization from cyclohexane affords a pure higher diamondoidone.

Example 17 Monohydroxylated Higher Diamondoids at the Secondary Carbonsfrom Higher Diamondoidones

A suitable higher diamondoidone is reduced with lithium aluminum hydride(a little excess) in ethyl ether at low temperatures. After completionof the reaction, the reaction mixture is worked up by adding saturatedNa₂SO₄ aqueous solution to decompose excess hydride at low temperature.Decantation from the precipitated salts gives a dry ether solution,which, when evaporated, affords a crude monohydroxylated higherdiamondoid at the secondary carbon. Further recrystallization fromcyclohexane gives a pure sample.

Example 18 Mononitration of Higher Diamondoids

A mixture of 0.05 mole of a higher diamondoid and 50 mL of glacialacetic acid is charged to a stirred stainless 100 mL autoclave, which ispressurized with nitrogen to a total pressure of 500 p.s.i.ga. After themixture is then heated to 140° C., 9.0 g (0.1 mole) of concentratednitric acid is introduced into the reaction zone by means of a feed pumpat a rate of 1-2 mL per minute. When the acid feed is completed, thereaction temperature is maintained at 140° C. for 15 minutes, afterwhich time the reaction mixture is cooled down to room temperature anddiluted with an excess of water to precipitate the products. Thefiltered solids is then slurried with a mixture of 10 mL of methanol, 15mL of water, and 1.7 g of potassium hydroxide for 18 hours at roomtemperature. After dilution with water, the alkali-insoluble material isextracted by light petroleum ether. The petroleum ether extracts iswashed by water and dried over anhydrous magnesium sulfate.Concentration of this solution affords a white solid. The aqueous alkalisolution from which the alkali-insoluble material had been extracted iscooled to 0-3° C. and neutralized by the dropwise addition of an aqueousacetic acid-urea mixture to regenerate some more products. GC analysisshows that the alkali-insoluble sample is mainly mononitro higherdiamondoid with a small amount of dinitro product as well as a fewunidentified components in minor quantities. The separation ofanalytically pure mononitro product from the other components of thealkali-insoluble product is difficult. However, by recrystallizationfrom methanol and repeated sublimation, a pure sample of mononitrohigher diamondoid is obtained.

Example 19 Mononitro Higher Diamondoids from Monoamino Compounds

A suspension of 0.01 mole of a suitable monoaminated higher diamondoidin 50 mL water is heated to 60° C. To this suspension a solution of 3.5g potassium permanganate in 50 mL water (about 1 hour) is graduallyadded dropwise. After this permanganate solution has been added, themixture is heated to reflux for about 2 hours, whereby the fractionsublimating in the condenser is washed back in again. At the end of thereaction, the crystals located in the condenser are rinsed out withdilute hydrochloric acid, stirred a little longer in the hydrochloricacid to remove the unreacted amine and filtered off. The crystals arepurified twice by sublimation under vacuum.

Example 20 Monocarboxylation of Higher Diamondoids

A mixture of 29.6 g (0.4 mole) tert-butanol and 55 g (1.2 mole) 99%formic acid is added dropwise over about 3 hours to a mixture of 470 g96% sulfuric acid and 0.1 mole higher diamondoid dissolved in 100 mLcyclohexane while stirring vigorously at room temperature. Afterdecomposing with ice, the acids are isolated and purified byrecrystallization from methanovwater giving the monocarboxylated higherdiamondoid. In addition to using cyclohexane one can also use n-hexaneas the solvent for the reaction. A test with only 50 mL cyclohexaneindicates a substantially worse yield.

Example 21 Monocarboxylated Higher Diamondoids from MonobrominatedCompounds

In 360 mL concentrated sulfuric acid, which has been cooled to +10° C.,is placed in a 1-L three-necked flask, which is equipped with a stirrer,a reflux condenser and an Anschütz top with two dropping funnels. Afterremoving the ice bath, while stirring, a suitable monobrominated higherdiamondoid (0.056 mole) dissolved in 25 mL dry, highly pure n-hexane and25.3 mL anhydrous formic acid is added dropwise into the flask in acourse of about 1 hour with the resulting reaction mixture turningreddish brown. A fume hood is necessary to remove the carbon monoxideproduced. After the dropwise addition has been completed, the mixture isvigorously stirred at room temperature for about an additional 2 hours.Then the reaction mixture is poured onto ice, whereby the acidprecipitates out of solution. After standing for an additional about 2hours, additional acid separates out. The acid is purified bydissolution in ether and extraction with dilute sodium hydroxide aqueoussolution. The acid which precipitates during the acidification isrecrystallized from dilute methanol.

Example 22 Monocarboxylated Higher Diamondoids from MonohydroxylatedCompounds

A monocarboxylated higher diamondoid can be formed using amonohydratedoxlated precursor. When a monohydroxylated higher diamondoidis used, one follows the procedure described in Example 24 above, exceptthat the amount of n-hexane must be increased to 150 mL due to the lowersolubility of the monohydroxalted higher diamondoid in n-hexane.

Example 23 Monochlorocarboxylated Higher Diamondoids from MonobrominatedCompounds

A mixture of a suitable monobrominated higher diamondoid (0.012 mole)and 9.0 g trichloroethylene is added dropwise over about 4 hours into 24mL 90% sulfuric acid at 103-106° C. while stirring. After the additionis completed, the mixture is stirred for about an additional 2 hours atthe specified temperature above. Then the mixture is cooled down andhydrolyzed with ground ice. The precipitated product can be freed fromthe neutral fraction by dissolution in dilute sodium hydroxide solutionand extraction with ethyl ether. When acidified with dilute hydrochloricacid solution, the carboxylic acid precipitates out of the alkalinesolution. Further purification could be achieved by recrystallizationfrom cyclohexane.

Example 24 Dicarboxylated Higher Diamondoids from DihydroxylatedCompounds

Formic acid (98%, 280 mL) is added dropwise to a stirred solution of adihydroxylated higher diamondoid (0.091 mol) in concentrated sulfuricacid (96%, 1.3 L) at 0° C. The mixture is stirred at 0° C. for about 2hours and then stirred at room temperature for about 4 hours, afterwhich the mixture is then poured over ice/water. The resultant productis washed with water and acetone and dried to afford the dicarboxylatedhigher diamondoid.

Example 25 Monoacetaminated Higher Diamondoids from MonobrominatedCompounds

A suitable monobrominated higher diamondoid (0.093 mole) is dissolved in150 mL acetonitrile. While stirring the mixture, 30 mL concentratedsulfuric acid is slowly added to the solution, whereby the mixture heatsup by reaction. After the mixture has been left standing for about 12hours, the solution is poured into 500 mL ice water, whereby themonoacetamino higher diamondoid separates out in high purity. Byneutralizing the filtrate an additional small amount of the reactionproduct can be obtained.

Example 26 Monoacetaminated Higher Diamondoids from MonohydroxylatedCompounds

A suitable monohydroxylated higher diamondoid (0.046 mole) is dissolvedin 120 mL highly pure glacial acetic acid and treated with 13 mLacetonitrile and 4 mL concentrated sulfuric acid. The reaction mixtureis left standing (closed) for about 20 hours at room temperature, andthen twice the volume of water is added to it. After a few hours theprecipitated reaction product is filtered off, and after drying it isrecrystallized from cyclohexane.

Example 27 Monoacetaminated Higher Diamondoids from MonocarboxylatedCompounds

Within 12 minutes, 4.1 g (0.1 mole) acetonitrile and a suitablemonocarboxylated higher diamondoid (0.018 mole) are added to 20 mL 100%sulfuric acid at room temperature while stirring vigorously. Ice isadded after about 1.5-hour post reaction. Then a precipitate isseparated out. The suspension is made basic with sodium hydroxidesolution and suctioned over a glass frit. Recrystallization fromcyclohexane affords the monoacetaminated higher diamondoid product.

Example 28 Monoformylaminated Higher Diamondoids from MonocarboxylatedCompounds

Within 7 minutes, 8.16 g (0.17 mole) sodium cyanide and a suitablemonocarboxylated higher diamondoid (0.028 mole) mixture is added to 100mL 100% sulfuric acid while stirring vigorously. After ½ hour,decomposition is carried out by pouring the reaction mixture onto 250 gcrushed ice which is then made basic by the addition of a sufficientamount of sodium hydroxide solution and extracted five times withbenzene/ether. The solvent is removed in vacuo from the combinedextracts and the residue is recrystallized from benzene/hexane to affordthe monoformylaminated higher diamondoid.

Example 29 Monoarylated Higher Diamondoids from Monobrominated Compounds

1.1 g sublimated iron(III) chloride and 20 mL absolute thiophene-freebenzene are placed in a 150-mL three-necked flask, which is equippedwith a stirrer, a reflux condenser and a dropping funnel. While stirringand heating the mixture in the steam bath, a solution of a suitablemonobrominated higher diamondoid (0.018 mole) in 30 mL benzene is addeddropwise to the above flask over about 30 minutes. The reaction mixtureis heated for about an additional 3 hours until the production ofhydrogen bromide drops off. This mixture is kept standing over night andpoured onto a mixture of ice and hydrochloric acid. The benzene phase isseparated out and the aqueous solution is extracted twice with benzene.The combined benzene extracts are washed several times with water anddried with calcium chloride. The residue solidifies upon cooling and iscompletely free of the solvent in vacuum. Recrystallization from a smallamount of methanol while cooling with CO₂/trichloroethylene and furthersublimation under vacuum afford the monoalkylated higher diamondoid.

Example 30 Monoethenylated Higher Diamondoids from MonobrominatedCompounds

Step 1: a solution of a suitable monobrominated higher diamondoid (0.046mole) in 15 mL n-hexane in a 150-mL three-necked flask (equipped with astirrer, a gas inlet tube and a gas discharge tube with a bubblecounter) is cooled to −20 to −25° C. in a cooling bath. While stirringthe flask 4.0 g powdered freshly pulverized aluminum bromide of highquality, and ethylene is added in such a way that the gas intake can becontrolled with the bubble counter. The reaction is completed afterabout 1 hour. The reaction solution is decanted from the catalyst andinto a mixture of ether and water. The ether layer is separated off,while the aqueous phase is extracted once more with ether. The combinedether extracts are washed with water and dilute sodium carbonate aqueoussolution. After they have been dried over calcium chloride, ether isdistilled off. The residue is separated by distillation under vacuumproviding crystals of the higher diamondoidyl ethyl bromide.

Step 2: a solution of 0.7 g fine powdered potassium hydroxide and theabove higher diamondoidyl ethyl bromide (0.012 mole) in 10 mL diethyleneglycol is heated to 220° C. in the oil bath for 6 hours. After coolingdown, the mixture is diluted with 30 mL water and exacted with ethylether. The ether extract is washed twice with water and dried overcalcium chloride. The residue left behind after the ether has beendistilled off is sublimated in vacuum, and if necessary for suitablepurity, the compound can be recrystallized from methanol.

Example 31 Monoethynylated Higher Diamondoids from MonobrominatedCompounds

Step 1: in a 150-mL two-necked flask with a stirrer and a drying tube, amixture of 0.069 mole of a suitable monobromonated higher diamondoid and20 mL vinyl bromide is cooled to −65° C. in a cooling bath. Whilestirring, 4.5 g powdered aluminum bromide is added in portions and themixture is stirred for an additional about 3 hours at the sametemperature. Then the reaction mixture is poured into a mixture of 30 mLwater and 30 mL ethyl ether. After vigorously stirring, the ether layeris separated and the aqueous layer is extracted once more with ether.The combined ether extracts are washed with water and dilute sodiumcarbonate solution. After it has been dried with calcium chloride andthe solvent has been distilled off, the residue is distilled undervacuum.

Step 2: 15 g powdered potassium hydroxide in 30 mL diethylene glycol isheated to reflux with 0.046 mole of the above product for about 9 hoursin the oil bath. The monoethynylated higher diamondoid compound which isformed, is then sublimated in the condenser and must be returned to thereaction mixture from time to time. At the end of the reaction time, thereaction mixture is distilled until no more solid particles go over. Thedistillate is extracted with ethyl ether and the ether phase is washedwith water and dried over calcium chloride. A short time after the etherhas been distilled off, the residue solidifies. This residue is thensublimated under vacuum and, if necessary, recrystallized from methanol.

Example 32 Mono- and Diethynylated Higher Diamondoids fromMonobrominated Compounds

A solution of a monobromo higher diamondoid (14.2 mmol) and vinylbromide (5 mL) in CH₂Cl₂ (25 mL) is cooled with a dry ice-acetone bath(−30° C.). To this mixture aluminum bromide (4.9 mmol) is added,portionwise, over 30 minutes while the internal temperature is keptbelow −24° C., then the mixture is stirred at −30° C. for 45 min.,diluted with CH₂Cl₂ and slowly poured over crushed ice and concentratedhydrochloric acid (20 mL). From this, the organic layer is separated andthe aqueous layer is extracted with CH₂Cl₂. The combined organic layersare washed with brine, dried and filtered. Solvent is evaporated underreduced pressure to give an oil.

The oil is dissolved in DMSO (50 mL) and potassium t-butoxide (36 mmol)is added over 1 hour. The mixture is stirred at room temperature for 3days and then heated at 50-55° C. for 3.5 hours. Standard isolationprocedures with CH₂Cl₂ gives an oil. Bulb to bulb distillation providesa semi-solid residue. The residue is chromatographed on silica gel(hexane and 95:5 hexane/CH₂Cl₂) to afford the mono- and diethynylatedhigher diamondoid.

Example 33 Higher Diamondoids Monocarboxylic-Acid Ethyl Ester fromActivated Monocarboxylated (Acid Chloride) Compounds

0.017 mole of a suitable monocarboxylated higher diamondoid is mixedwith 4.2 g PCl₅ in a 50-mL flask with a stirrer and a reflux condenser.The reaction starts after approximately 30-60 seconds with liquefactionof the reaction mixture. The mixture is heated for about 1 hour whilestirring the flask on the steam bath. The POCl₃ formed is distilled offunder vacuum. The acid chloride left behind as a residue is cooled withice water, and 6.0 mL absolute ethanol is added dropwise. This mixtureis heated about an additional 1 hour on the steam bath allowed to cooland then poured into 50 mL. The ester is taken up with ethyl ether andthen washed with potassium carbonate aqueous solution and water. Afterdrying, fractionation is carried out over calcium chloride under vacuum.

Example 34 Diesterified Higher Diamondoids from Dihydroxylated Compounds

To 2 mL of dioxane is added a dihydroxylated higher diamondoid (1.0mmol) and triethylamine (2.2 mmol) at a temperature of 50° C. Theresultant mixture is added dropwise to a solution of acrylic acidchloride (2.2 mmol) in dioxane (2 mL). The mixture is maintained at 50°C. for about 1 hour. Until the desired diacrylate is formed, thecompound is isolated using standard methods.

Example 35 Monomethylhydroxylated Higher Diamondoids from MonoesterifiedCompounds

0.014 mole of a suitable higher diamondoid monocarboxylic acid-ethylester dissolved in 10 mL absolute ether. This mixture is slowly addeddropwise, to a room temperature stirred suspension of 0.8 g lithiumalanate in 16 mL absolute ether. This mixture is stirred for anadditional about 1 hour and then water is carefully added. The ethersolution is separated out and the aqueous phase is extracted with ethertwo more times. After the combined extracts have been dried with calciumchloride, the ether is distilled off and the residue is recrystallizedfrom methanol/water.

Example 36 Monoaminated Higher Diamondoids from MonoacetaminatedCompounds

A suitable monoacetaminated higher diamondoid (0.015 mole) is heated toreflux for about 5 hours with a solution of 6 g powdered sodiumhydroxide in 60 mL diethylene glycol. After it has been cooled down, themixture is poured into 150 mL water and extracted with ethyl ether. Theether extract is dried with potassium hydroxide. The ether is distilledoff and the residue is sublimated to afford the product monoaminatedhigher diamondoid.

Example 37 Monoaminated Higher Diamondoids from Mononitro Compounds

A mixture of 0.412 mmol of a mononitro higher diamondoid and 11.5 g ofsodium sulfide nonahydrate in 400 mL of mixed solvent of THF/H₂O (3:2v/v) is vigorously stirred for about 12 hours at 75° C. After cooling toroom temperature, the mixture is concentrated below 40° C. under reducedpressure until the volume is reduced to about 15 mL. The precipitate isfiltered with suction followed by washing well with water and a 1.0 NHCl aqueous solution. This crude product is dissolved in chloroform orethyl ether and washed with water (4×80 mL) to neutralize any sodiumhydroxide in the organic phase (chloroform or ether) until the materialis essentially free from sodium hydroxide and/or sodium chloride. Afterremoval of the solvent, a crude product is obtained. The separation andpurification of the product is carried out with column chromatography onneutral Al₂O₃ using chloroform/hexane as the eluent, to yield a puremonoaminated higher diamondoid. If necessary, further purification withcolumn chromatography could be repeated for several times.

Example 38 Monoaminated Higher Diamondoids from MonochlorinatedCompounds

A suitable monochlorinated higher diamondoid is converted by theacetonitrile-sulfuric acid procedure described above, to themonoacetaminated higher diamondoid. The crude amide, without priorpurification, is saponified to afford a monoaminated higher diamondoid.Purification of the amine as described above gives a pure monoaminatedhigher diamondoid.

Example 39 Monoaminated Higher Diamondoids from MonocarboxylatedCompounds

Step 1: 0.017 moles of a suitable monocarboxylated higher diamondoid ismixed with 4.2 g PCl₅ in a 50-mL flask equipped with a stirrer and areflux condenser. The reaction starts after 30-60 seconds withliquefaction of the reaction mixture. The mixture is heated for anadditional hour while stirring on a steam bath. The POCl₃ formed duringthe reaction is distilled off under vacuum to afford an acid chloride.

Step 2: a solution of the above higher diamondoidyl monocarboxylicacid-chloride (0.027 mole) in 12 mL absolute tetrahydrofuran is slowlyadded dropwise to a 60 mL of a concentrated aqueous ammonia solution,while stirring and cooling the mixture with ice water. The amide (higherdiamondoidyl monocarboxylic acid-amide) is then separated out of themixture as a precipitate. The precipitate is suctioned, washed well withwater and recrystallized from cyclohexane after it has been dried.

Step 3: 0.018 mole of the above amide is dissolved in 25 mL absolutemethanol. This solution is added to a solution of 1.0 g sodium in 25 mLabsolute methanol, in a 150-mL three-necked flask with a stirrer, areflux condenser and dropping funnel. To this flask 1.0 mL bromine isadded dropwise with ice cooling, and then the mixture is slowly heatedto around 55° C. (water bath temperature). After the mixture has beencooled, water is added and the precipitate is separated out byfiltration. Further purification can be achieved by recrystallizationfrom ethanol.

Step 4: the above product is finally saponified and worked up in thesame way as described above to afford the target compound.

Example 40 Monoaminated Higher Diamondoids from Monobrominated Compounds

Step 1: a monobromo higher diamondoid (0.028 mol) is mixed with 40 in mLformamide. The resultant mixture is refluxed for about 12 hours. Aftercooling, the reaction mixture is poured into water and extracted withdichloromethane. The organic phase is dried with magnesium sulfate,filtered, and evaporated to dryness under vacuum to provide a monoN-formyl higher diamondoid.

Step 2: the above mono N-formyl higher diamondoid (0.023 mol) is mixedwith 100 mL of 15% hydrochloric acid. The resultant mixture is heated toboiling for about 24 hours. After cooling, the precipitate is filteredand recrystallized from isopropanol to afford the monoamino higherdiamondoid.

Example 41 2,2-Bis(4-hydroxyphenyl) Higher Diamondoids from KetoCompounds

A flask is charged with a mixture of a higher diamondoidone (0.026mole), phenol (16.4 g, 0.17 mole), and butanethiol (0.15 mL). Heat isapplied and when the reaction mixture becomes liquid at about 58° C.,anhydrous hydrogen chloride is introduced until the solution becomessaturated. Stirring is continued at about 60° C. for several hours,during which period a solid forms. The solid obtained is filtered off,washed with dichloromethane and dried to afford the bisphenol higherdiamondoid product. This product is purified by sublimation afterrecrystallization from toluene.

Example 42 2,2-Bis(4-aminophenyl) Higher Diamondoids from Keto Compounds

A higher diamondoidone (0.041 mole) in solution with 15 mL of 35% HClaqueous solution housed in a 100 mL autoclave is combined with excessaniline (15.7 g, 0.17 mole) and the mixture is stirred at about 120° C.for about 20 hours. After cooling, the solution is made basic withaddition of a NaOH aqueous solution to pH 10. The resulting oily layeris separated and distilled to remove the unreacted excess aniline. Theresidual crude product is recrystallized from benzene to afford thehigher diamondoid derived bisphenylamine.

Example 43 2,2-Bis[4-(4-aminophenoxy)phenyl] Higher Diamondoids fromBisphenol Higher Diamondoids

A mixture of a 2,2-bis(4-hydroxyphenyl) higher diamondoid (0.01 mole),p-fluoronitrobenzene (3.1 g, 0.022 mole), potassium carbonate (3.31 g,0.024 mole) and N,N,-dimethylacetamide (DMAc, 10 mL) is refluxed forabout 8 hours. The mixture is then cooled and poured into aethanol/water mixture (1:1 by volume). The crude product is crystallizedfrom DMF to provide the 2,2-bis[4-(4-nitrophenoxy)phenyl] higherdiamondoid.

Hydrazine monohydrate (20 mL) is added dropwise to a mixture of theabove product (0.002 mole), ethanol (60 mL), and a catalytic amount of10% palladium on activated carbon (Pd/C, 0.05 g) at the boilingtemperature. The reaction mixture is refluxed for about 24 hours, andthe product 2,2-Bis[4-(4-aminophenoxy)phenyl] higher diamondoid isprecipitated during this period. This mixture is then added to enoughethanol to dissolve the product and filtered to remove Pd/C. Aftercooling, the precipitated crystals are isolated by filtration andrecrystallized from 1,2-dichlorobenzene.

Example 44 [Higher Diamondoid-Higher Diamondoid] from MonobromonatedHigher Diamondoid

A suitable monobrominated higher diamondoid (50 mmole) is dissolved in30 mL of xylene and heated to reflux in a three-necked flask fitted withthermometer, nitrogen inlet, stirrer, and reflux condenser, under a slowstream of nitrogen. Then a total of 1.15 g of small pieces of sodiummetal is added to the stirred reaction mixture over a period of about 4hours. After all sodium has been added, the mixture is refluxed forabout an additional hour and then filtered in the hot state. On coolingto room temperature, the product higher diamondoid covalently bonded toa higher diamonoid is crystallized from the filtrate. Condensation ofthe filtrate provides some additional amount of the product.Recrystallization from benzene gives a pure sample. Alternatively, usingthe same procedure as above, a dibromonated higher diamondoid is used toform a three diamondoid product.

Example 45 Dibromination of Higher Diamondoid-Higher Diamondoidforproduction of Higher Diamondoid Polymer

A suitable higher diamondoid covalently bonded to another higherdiamondoid (14 mmole) is charged into a round-bottom flask fitted with along reflux condenser. Then 20 mL of bromine is added with stirring, andhydrogen bromide is formed. Hydrobromic acid evolution ceases afterabout 15 min. the reaction mixture is then heated to reflux (ca. 61° C.pot temperature) for about 2 hours. The cooled reaction product isdiluted with 75 mL of CCl₄ and transferred to a separatory funnel. TheCCl₄ is then shaken with ice-water, and sodium bisulfite is added untilexcess bromine is destroyed. The organic layer is separated and thewater layer is extracted twice with 50 mL of CCl₄. The combined organicsolution is dried over sodium sulfate and the solvent is stripped underslight vacuum. The reaction product in the pot is precipitated withmethanol, filtered off, and recrystallized from dioxane to give aBr-[Higher Diamondoid-Higher Diamondoid]-Br product. Such a reaction canbe continued to form a higher diamondoid polymer.

Example 46 Polymerization of Diacrylated Higher Diamondoids

The following compositions are subjected to polymerization: diacrylatedhigher diamondoid; monoacrylated higher diamondoid; a 50:50 mixture byweight of monoacrylated higher diamondoids and methyl methacrylate; and,a 50:50 mixture by weight of monoacrylated higher diamondoid anddiethylene glycol bis allylcarbonate. To the various compositions isadded 0.1 part by weight of a photo-polymerization initiator(benzophenone). The mixture is applied to a glass plate andphoto-polymerized by irradiation with ultraviolet light.

Example 47 Polymerization of Diethynylated Higher Diamondoids

A sample of a diethynylated higher diamondoid (275 mg) is sealed in aglass tube and heated to 200° C. for 14 hours and at 250° C. for 48hours. The tube is cooled to room temperature and opened to afford apolymeric resin.

Example 48 Copolymerization of Monoethynylated Higher Diamondoids andDiethynylated Compounds

A mixture of a monoethynylated higher diamondoid (55% by weight) anddiethynylated higher diamondoid (45% by weight) is sealed in a tube andheated at 175° C. for 2 hours, 200° C. for 14 hours, 210° C. for 8hours, 225° C. for 48 hours and at 250° C. for 16 hours. The tube isthen cooled to room temperature and opened to give a polymeric resin.

Example 49 Polyesters Derived from 2,2-Bis(4-hydroxyphenyl) HigherDiamondoids by Solution Polycondensation

A 2,2-bis(4-hydroxyphenyl) higher diamondoid (0.005 mole) is mixed withpyridine (2 mL) at room temperature for about 20 minutes. Terephthaloylchloride (1.015 g, 0.005 mole) in nitrobenzene (20 mL) is added to theabove solution at room temperature for about 5 minutes and then themixture is heated to about 150° C. for about 10 hours. The resultingpolymer solution is poured into methanol to precipitate the polymer. Thepolymer is washed with hot methanol, collected on a filter, and dried invacuo at about 60° C. for about 24 hours.

Example 50 Polyamides Derived from 2,2-Bis[4-(4-aminophenoxy)phenyl]Higher Diamondoids by Solution Polycondensation

A flask is charged with a mixture of a 2,2-bis[4-(4-aminophenoxy)phenyl]higher diamondoid (0.9 mmol), terephthalic acid (0.149 g, 0.9 mmol),triphenyl phosphite (0.7 mL), pyridine (0.6 mL), N-methyl-2-pyrrolidone(NMP, 2 mL) and calcium chloride (0.25 g). It is refluxed under argonfor about 3 hours. After cooling, the reaction mixture is poured into alarge amount of methanol with constant stirring, producing a precipitatethat is washed thoroughly with methanol and hot water, collected on afilter, and dried to afford a polyamide containing higher diamondoidcomponents along the polymer chain.

Example 51 Polyimides Derived from 2,2-Bis[4-(4-aminophenoxy)phenyl]Higher Diamondoids by Chemical Imidization

To a stirred solution of a 2,2-bis[4-(4-aminophenoxy)phenyl] higherdiamondoid (1.2 mmol) in DMAc (7 mL) is gradually added pyromelliticdianhydride (0.262 g, 1.2 mmol). The mixture is stirred at roomtemperature for 2-4 hours under argon atmosphere to form the poly(amicacid). Imidization is carried out by adding DMAc and an equimolarmixture of acetic anhydride and pyridine into the above-mentionedpoly(amic acid) solution with stirring at room temperature for about 1hour and then heating at about 100° C. for an additional about 3 hours.The reaction product is subsequently poured into methanol and theprecipitate is filtered off, washed with methanol and hot water, anddried to afford the polyimide containing higher diamondoid componentsalong the polymer chain.

Example 52 Polyimides Derived from 2,2-Bis(4-aminophenyl) HigherDiamondoids by Chemical Imidization

To a solution of a 2,2-bis(4-aminophenyl) higher diamondoid (5 mmol) in17.9 mL of NMP, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA,98.6%, 1.61 g, 5 mmol) is added with a solid content of 15 wt %. Thesolution is continuously stirred at room temperature for about 24 hours.To the reaction mixture are added 1.5 mL of acetic anhydride and 2.0 mLof pyridine and then the temperature is raised to about 120° C. and keptat this temperature for about 3 hours. The resulting solution is pouredinto excess methanol and filtered. The precipitated polymer is washedseveral times with water and methanol, and then the polymer is dried atabout 100° C. for around 12 hours in vacuo.

Example 53 Polyimides Derived from 2,2-Bis(4-aminophenyl) HigherDiamondoids by Solution Polymerization

To a solution of a 2,2-bis(4-aminophenyl) higher diamondoid (5 mmol) in19 mL of freshly distilled m-cresol,3,3′,4,4′-benzophenonetetracarboxylic dianhydride (98.6%, 1.61 g, 5mmol) and isoquinoline (0.95 mL) as a catalyst are added at roomtemperature under nitrogen atmosphere. The reaction mixture is heated toabout 70˜80° C. over 2 hours and kept at this temperature for about 2hours. Afterwards, the solution temperature is slowly raised to about200° C. over 2 hours and refluxed for 6 hours. The polymerization isperformed under a gentle nitrogen stream to remove the water producedduring imidization. Work-up is done by pouring the resulting solutioninto excess methanol and filtering. The precipitated polymer is washedseveral times with water and methanol, and then the polymer is dried atabout 100° C. for around 12 hours in vacuo.

Example 54 Linear Polyaspartimides Derived from2,2-Bis[4-(4-aminophenoxy)phenyl] Higher Diamondoids by the MichaelAddition Reaction

In a 100 mL three necked flask equipped with a magnetic stirrer, areflux condenser, thermometer and nitrogen inlet, 0.553 g (1.25 mmol) ofbis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BEMM) is added to 3.5 mLof m-cresol. When all the BEMM is dissolved, 1.25 mmol of a diamine2,2-bis[4-(4-aminophenoxy)phenyl] higher diamondoid is added. Then 0.1mL of glacial acetic acid, used as a catalyst, is added into the mixtureso that the above diamine is completely dissolved. The reaction mixtureis then immersed in an oil bath maintained at 100-110° C. for about 100hours to polymerize. The resulting polymer is isolated by pouring theviscous reaction mixture into excess ethanol under vigorous stirring.The polymer precipitate is collected by filtration and washed thoroughlywith ethanol and extracted with hot ethanol using a Soxhlet extractorand subsequently dried in a vacuum oven at 70° C. for about 24 hours.

Example 55 4-(1-Higher Diamondcidyl)-1,3-Benzenediols from BrominatedCompounds

A suitable brominated higher diamondoid (0.046 mole), resorcinol (5.51g, 0.05 mole), and benzene (50 mL) are combined in a reaction flaskequipped with a nitrogen inlet, a condenser fitted with a causticscrubber, and a stirrer. This mixture is heated to reflux and for about72 hours to allow for reaction under a constant nitrogen purge to assistin the removal of HBr formed. The reaction mixture is cooled to ambienttemperature and the higher diamondoidyl substituted resorcinol iscrystallized from solution. Residual resorcinol is removed byprecipitating a solution of the product in methanol into warm waterfollowed by filtrating and washing with water. Subsequent purificationto a polymerization quality monomer is accomplished by vacuum drying toremove residual water, recrystallizing from toluene, and finallysubliming to afford the product.

Example 56 4-(1-Higher Diamondoidyl)-1,3-Bis(4-aminophenoxy)benzene from4-(1-Higher Diamondoidyl)-1,3-Benzenediol

A mixture of a 4-(1-higher diamondoidyl)-1,3-benzenediol (13 mmol),p-chloronitrobenzene (4.53 g, 28.8 mmol), potassium carbonate (4.3 g,31.2 mmol) and dry N,N-dimethylformamide (DMF, 30 mL) is refluxed forabout 8 hours. The mixture is then cooled and poured into amethanol-water solution (1:1 by volume). The crude product isrecrystallized from glacial acetic acid.

Hydrazine monohydrade (10 mL) is added dropwise to a mixture of theabove product (4-(1-higher diamondoidyl)-1,3-bis(4-nitrophenoxy)benzene,12.3 mmol), ethanol (25 mL), and a catalytic amount of 10% palladium onactivated carbon (Pd/C, 0.05 g) at the boiling temperature. The reactionmixture is refluxed for about 24 hours, and the diamine product isprecipitated during this period. The mixture is then added to asufficient amount of ethanol to dissolve the diamine product andfiltered to remove Pd/C. After cooling, the recipitated crystals areisolated by filtration and recrystallized from 1,2-dichlorobenzene toafford a pure diamine product.

Example 57 4-(1-HigherDiamondoidyl)-1,3-Bis(4-trimellitimidophenoxy)benzene from 4-(1-HigherDiamondoidyl)-1,3-Bis(4-aminophenoxy)benzene

A flask is charged with 1.73 mmol of a 4-(1-higherdiamondoidyl)-1,3-bis(4-aminophenoxy)benzene, 0.68 g (3.54 mmol) oftrimellitic anhydride, and 5 mL of DMAc. The mixture is stirred at roomtemperature for about 5 hours under argon atmosphere. While continuingto maintain agitation and room temperature, 2.4 mL of acetic anhydrideand 1.5 mL of pyridine are added incorporating for about 1 hour.Afterwards the mixture is heated at 100° C. for about 4 hours and thencooled and poured into methanol. The precipitate is filtered off and ispurified by extraction with hot ethanol using a Soxhlet extractor andsubsequently dried in a vacuum oven at 70° C. for 24 hours to afforddiimide-dicarboxylic acid: 4-(1-higherdiamondoidyl)-1,3-bis(4-trimellitimidophenoxy)benzene.

Example 58 Polyamide-imides Derived from 4-(1-HigherDiamondoidyl)-1,3-Bis(4-trimellitimidophenoxy)benzene by SolutionPolycondensation

A mixture of the diimide-dicarboxylic acid (4-(1-higherdiamondoidyl)-1,3-bis(4-trimellitimidophenoxy)benzene, 0.7 mmol), 0.362g of a diamine (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 0.7mmol), 0.25 g of calcium chloride, 0.6 mL of triphenyl phosphite, 0.6 mLof pyridine, and 3.0 mL of NMP is heated with stirring at 100° C. forabout 2 hours under argon stream. After cooling, the reaction mixture ispoured into a large amount of methanol with constant stirring, producinga precipitate that is washed thoroughly with hot water and methanol,collected on a filter, and dried at 100° C. under vacuum for 24 hours toafford a pure polyamideimide containing higher diamondoid components inthe polymer backbone.

Example 59 Poly(aryl ethers) Derived from 4-(1-Higher Diamondoidyl)-1,3-Benzenediols by Nucleophilic Aromatic Substitution Polymerization

A 4-(1-higher diamondoidyl)-1,3-benzenediol (20.5 mmol) and4,4′-difluorobenzophenone (4.468 g, 20.5 mmol) mixture is dissolved in35 mL DMAc and 10 mL toluene in a reaction flask fitted with a nitrogenblanket, mechanical stirrer, and a Dean-Stark trap. To this mixtureK₂CO₃ (2.969 g, 21.48 mmol) is added while stirring and heating toreflux. Reflux is held at around 130° C. for about 1 hour followed bythe gradual removal of toluene from the reaction flask until the flasktemperature reaches around 160° C. (ca. 2 hours). The reaction mixtureis maintained at 160° C. for 10 hours and then cooled to ambienttemperature. The polymer solution is diluted with chloroform, filteredto remove the inorganic salts, acidified, and then precipitated intomethanol. Filtration and drying of the product at about 120° C. undervacuum gives the homopolymer.

Example 60 Co-Polymerization from 4-(1-HigherDiamondoidyl)-1,3-Benzenediols and 2,2-Bis(4-Hydroxyphenyl)propane byNucleophilic Aromatic Substitution

Co-polymerizations are carried out with different molar ratios ofcomonomers (2,2-bis(4-hydroxyphenyl)propane and a 4-(1-higherdiamondoidyl)-1,3-benzenediol) using either DMAc or tetramethylenesulfone (sulfolane) as solvent. For instance, a 4-(1-higher diamondoilyl)1.3-benzenediol (10.25 mmol) and 2,2-bis(4-hydroxyphenyl)propane(10.25 mmol) and 4,4′-difluorobenzophenone (4.468 g, 20.5 mmol) can bedissolved in 35 mL DMAc and 10 mL toluene in a reaction flask fittedwith a nitrogen blanket, mechanical stirrer, and a Dean-Stark trap. Tothis mixture K₂CO₃ (2.969 g, 21.48 mmol) is added while stirring andheating to reflux. Reflux is held at around 130° C. for about 1 hourfollowed by the gradual removal of toluene from the reaction flask untilthe flask temperature reaches around 160° C. (ca. 2 hours). The reactionmixture is maintained at 160° C. for 10 hours and then cooled to ambienttemperature. The polymer solution is diluted with chloroform, filteredto remove the inorganic salts, acidified, and then precipitated intomethanol. Filtration and drying of the product at about 120° C. undervacuum gives the copolymer. If sulfolane is used as the solvent, theco-polymers are Soxhlet extracted with methanol to remove solvent andsalts from the insoluble polymer.

Example 61 Poly(3-benzyloxypropyl malate-co-ethyl Higher DiamondylMalate (85/15) from 3-Benzyloxypropylmalolactonate and Ethyl HigherDiamondoidyl Malolactonate by Anionic Ring-Opening Co-Polymerization

A flask is charged with a mixture of 3-benzyloxypropylmalolactonate (85mol %), ethyl higher diamondoidyl malolactonate (15 mol %) andtetraethylammonium benzoate (10⁻³ eq. per mole of total moles of theco-monomers, acting as an initiator of the anionic ring-openingco-polymerization) under nitrogen. The mixture is then well stirred andwarmed to 37° C. under nitrogen atmosphere and is maintained at thistemperature for 15 days. After completion of the co-polymerizationreaction, the copolymers are collected and washed with small amount ofwater, ethanol, and dried in vacuum for about 24 hours.

Example 62 Higher Diamondoidyl Propenyl Ether from MonohydroxylatedCompounds

To a 150 mL round bottom flask are added a monohydroxylated higherdiamondoid (2 mmol) and 3-bromo-1-propene (2 mmol) and 50 mL dry DMSO.The mixture is stirred and heated to about 100° C. under nitrogenatmosphere for a few hours. After completion of the reaction, thereaction mixture is poured into water (50 mL) and is extracted withethyl ether or chloroform (3×50 mL). The combined organic layer iswashed with water, dried over anhydrous Na₂SO₄, filtered, and thesolvent is evaporated to give a crude product. The resulting crudeproduct is purified by chromatography to afford higher diamondoidylpropenyl ether monomer suitable for polymerization.

Example 63 Higher Diamondoidyl Propynyl Ether from monohydroxylatedCompounds

To a 150 mL round bottom flask the following is added, amonohydroxylated higher diamondoid (2 mmol), a 3-bromo-1-propyne (2mmol), and 50 mL dry DMSO. The mixture is stirred and heated to about100° C. under nitrogen atmosphere for a few hours. After completion ofthe reaction, the reaction mixture is poured into water (50 mL) andextracted with ethyl ether or chloroform (3×50 mL). The combined organiclayer is washed with water, dried over anhydrous Na₂SO₄, filtered, andthe solvent evaporated to give a crude product. The resulting crudeproduct is purified by chromatography to afford higher diamondoidylpropynyl ether monomer suitable for polymerization.

Example 64 Higher Diamondoidyl Acryloyl Ester from monohydroxylatedCompounds

To a 150 mL round bottom flask the following is added, amonohydroxylated higher diamondoid (2 mmol) and acryloyl chloride (2mmol) and 50 mL dry THF. The mixture is stirred and heated to refluxunder nitrogen atmosphere for a few hours. After completion of thereaction, the solvent is evaporated to dryness and the resulting crudeproduct is purified by chromatography to afford higher diamondoidylacryloyl ester monomer suitable for polymerization.

Example 65 Higher Diamondoidyl Monocarboxylic-Acid Propenyl Ester fromActivated Monocarboxylic (Acid Chloride) Compounds

0.017 mole of a suitable monocarboxylated higher diamondoid is mixedwith 4.2 g PCl₅ in a 50-mL flask equipped with a stirrer and a refluxcondenser. The reaction starts after 30-60 seconds with liquefaction ofthe reaction mixture. The mixture is heated for an additional about 1hour while stirring on a steam bath. The POCl₃ formed during reaction isdistilled off under vacuum. The remaining acid chloride residue iscooled with ice water and 2-propen-1-ol (0.017 mole) is added dropwise.The mixture is heated for an additional 1 hour on a steam bath, cooled,and then poured into 50 mL water. The ester is taken up with ethyl etherand then washed with an aqueous potassium carbonate solution and water.After drying, fractionation is carried out over calcium chloride andunder vacuum to afford propenyl ester suitable for polymerization.

Example 66 Higher Diamondoidyl Monocarboxylic-Acid Propynyl Ester fromActivated Monocarboxylic (Acid Chloride) Compounds

0.017 mole of a suitable monocarboxylated higher diamondoid is mixedwith 4.2 g PCl₅ in a 50-mL flask equipped with a stirrer and a refluxcondenser. The reaction starts after 30-60 seconds with liquefaction ofthe reaction mixture. The mixture is heated for an additional about 1hour while stirring on a steam bath. The POCl₃ formed is distilled offunder vacuum. The acid chloride left behind as a residue is cooled withice water, and dropwise 2-propyn-1-ol (0.017 mole) is added. The mixtureis heated for an additional 1 hour on the steam bath, cooled and thenpoured into 50 mL water. The ester is taken up with ethyl ether and thenwashed with potassium carbonate aqueous solution and water. Afterdrying, fractionation is carried out over calcium chloride under vacuumto afford propynyl ester monomer suitable for polymerization.

Example 67 Higher Diamondoidyl Monocarboxylic-Acid Propenyl Amide fromActivated Monocarboxylic (Acid Chloride) Compounds

0.017 mole of a suitable monocarboxylated higher diamondoid is mixedwith 4.2 g PCl₅ in a 50-mL flask equipped with a stirrer and a refluxcondenser. The reaction starts after 30-60 seconds with liquefaction ofthe reaction mixture. The mixture is heated for an additional 1 hourwhile stirring on a steam bath. The POCl₃ formed is distilled off undervacuum. The resulting acid chloride residue is cooled with ice water,and 3-amino-1-propene (0.017 mole) is added dropwise. The mixture isheated for an additional 1 hour on the steam bath, cooled and thenpoured into 50 mL water. The amide is taken up with ethyl ether and thenwashed with potassium carbonate aqueous solution and water. Afterdrying, purification of the crude amide is conducted by chromatographyto afford propenyl amide suitable for polymerization.

Example 68 Higher Diamondoidyl Monocarboxylic-Acid Propynyl Amide fromActivated Monocarboxylic (Acid Chloride) Compounds

0.017 mole of a suitable monocarboxylated higher diamondoid is mixedwith 4.2 g PCl₅ in a 50-mL flask equipped with a stirrer and a refluxcondenser. The reaction starts after 30-60 seconds with liquefaction ofthe reaction mixture. The mixture is heated for an additional 1 hourwhile stirring on a steam bath. The POCl₃ formed is distilled off undervacuum. The acid chloride left behind as a residue is cooled with icewater, and 3-amino-1-propyne (0.017 mole) is added dropwise. The mixtureis heated for an additional 1 hour on the steam bath, cooled, and thenpoured into 50 mL water. The amide is taken up with ethyl ether and thenwashed with potassium carbonate aqueous solution and water. Afterdrying, purification of the crude amide is conducted by chromatographyto afford propynyl amide suitable for polymerization.

Example 69 Monoacryloylaminated Higher Diamondoids from MonoaminatedCompounds

To a 150 mL round bottom flask are added a monoaminated higherdiamondoid (2 mmol) and acryloyl chloride (2 mmol) and 50 mL dry THF.The mixture is stirred and heated to reflux under nitrogen atmospherefor a few hours. After completion of the reaction, which is convenientlymonitored by TLC or GC analysis, the solvent is evaporated to drynessand the resulting crude product is purified by chromatography to affordhigher diamondoidyl acryloyl amide monomer suitable for polymerization.

Example 70 Higher Diamondoidyl Propenyl Amide from MonoaminatedCompounds

To a 150 mL round bottom flask the following is added, a monoaminatedhigher diamondoid (2 mmol) and 3-bromo-1-propene (2 mmol) and 50 mL dryDMSO. This mixture is stirred and heated to reflux under nitrogenatmosphere for a few hours. After completion of the reaction, which isconveniently monitored by TLC or GC analysis, the reaction mixture ispoured into water (50 mL) and extracted with ethyl ether or chloroform(3×50 mL). The combined organic layer is washed with water, dried overanhydrous Na₂SO₄, filtered, and the remaining solvent is evaporated togive a crude product. The resulting crude product is purified bychromatography to afford higher diamondoidyl propenyl amide monomersuitable for polymerization.

Example 71 Higher Diamondoidyl Propynyl Amide from MonoaminatedCompounds

To a 150 mL round bottom flask the following is added, a monoaminatedhigher diamondoid (2 mmol) and 3-bromo-1-propyne (2 mmol) and 50 mL dryDMSO. The mixture is stirred and heated to reflux under nitrogenatmosphere for a few hours. After completion of the reaction, which isconveniently monitored by TLC or GC analysis, the reaction mixture ispoured into water (50 mL) and extracted with ethyl ether or chloroform(3×50 mL). The combined organic layer is washed with water and driedover anhydrous Na₂SO₄, filtered, and the solvent is evaporated to give acrude product. The resulting crude product is purified by chromatographyto afford higher diamondoidyl propynyl amide monomer suitable forpolymerization.

Example 72 Phenyl Higher Diamondoid-Modified PEGs [Poly(ethyleneglycol)s] from Alcoholate of Higher Diamondoidylphenol

To a stirred solution of a poly(ethylene gylcol) (PEG, 1 mmol) in 15 mLdichloromethane, 1 mL of triethylamine is added. This solution is cooledin an ice bath under nitrogen atmosphere. Then 1 g of4-toluenesulfonylchloride (5.2 mmol) is added. The reaction is continuedst 0° C. for 2 hours and then the mixture stirred at room temperatureovernight. The product is precipitated in diethyl ether. An additionalrecrystallization from ethanol is performed in order to remove thetriethylammonium chloride formed during the reaction according a purePEG tosylate.

Under a nitrogen atmosphere, a higher diamondylphenol (4 mmol) dissolvedin 70 mL of freshly distilled dichloromethane is added dropwise to 0.24g of sodium hydride suspended in 30 mL of distilled dichloromethane. Thesolution is stirred for 2 hours at room temperature before addingdropwise the PEG tosylate (a little excess) dissolved in 50 mL ofdichloromethane. The reaction mixture is kept at 40° C. for 24 hour. Theobtained polymer is precipitated in ethyl ether, recrystallized fromethanol and stored at 4° C.

Example 73 Design of Diamonds Containing Polymers or Co-Polymers

Polymers such as polyamides, polyimides, polyesters, polycarbonateswhich are easily processed soluble, mechanically strong and thermallystable are very important materials in wide range of industries, such asthe microelectronics industry. Introduction of different pendant groupssuch as cardo groups along the polymer backbone has been shown to impartgreater solubility and enhanced rigidity as well as better mechanicaland thermal properties of the resulting polymers. Of particular interestis introducing cage hydrocarbons into the polymer chain because suchcardo groups show significant characteristics such as highcardo/hydrogen ratio, high thermal and oxidative stability, rigidity,hydrophobicity, and transparency. Previous studies involved theintroduction of only adamantyl groups because of the limitedavailability of other lower diamondoid hydrocarbons (diamantane andtriamantane) and the unavailability of higher diamondoid hydrocarbons(tetramantane, pentamantane, hexamantane and the like). Incorporation ofadamantyl groups into the polymer backbone resulted in greatimprovements in the solubility, thermal stability and other physicalproperties of the resulting polymers. We now describe a series ofpolymers and co-polymers containing higher diamondoid hydrocarbonmoieties in the polymer backbone with improved physical properties andprocessability. It should be pointed out that only examples based oniso-tetramantane are given below in Examples 74-79. This does not meanthat iso-tetramantane is the only choice for these applications. Allother higher diamondoids and their isomers and/or their multifunctionalderivatives are good candidates for such applications.

Example 74 Water Soluble Poly)ethylene glycol)s (PEGs) Containing HigherDiamondoids for Potential Drug Delivery Purposes

Host-guest interactions are very important processes in human biology.The water solubility of drugs is a key factor in determining theirmedical efficacy in living tissue. In order to enhance drug efficiency,poly(ethylene glycol)s (PEGs) can be modified by higher diamondoidhydrocarbon compounds at their OH terminal ending(s). These hydrophobicgroups may be selected based upon their potentially strong interactionswith other groups in “cavities” formed in PEG polymer chains and thuscan help deliver the drugs which have low solubility in water. Examplesare shown in FIG. 35.

Example 35 Carbon-Rich Polymers for Nanolithography

Rapid advances in the miniaturization of microelectronic devices requirethe development of new imageable polymeric materials for 193 nmmicrolithography (The National Technology Roadmap for Semiconductors,Semiconductor Industry Association (SIA), San Jose, Calif., 1997). Thedesign challenge for 193 nm resist materials is the trade-off betweenplasma-etch resistance (which requires a high carbon/hydrogen ratio inthe polymer structure) and optical properties for lithographicperformance.

In FIG. 36 we show the design of a carbon-rich cyclopolymerincorporating both imageable functionalities (tert-butyl esters) forchemical amplification, and high etch-resistance moieties (higherdiamondoids such as tetramantanes, pentamantanes, hexamantanes and thelike). To adjust the physical properties of polymers, such aswettability and adhesion properties, a wide range of co-polymers can beprepared. This was shown to be feasible for adamantine-containingcyclopolymers and co-polymers by D. Pasini, E Low and J. M. J. Fréchet(Advanced Materials, 12, 347-351 (2000)), and those materials showedexcellent imaging properties. In addition, since the synthetic routesinvolve free radical polymerization techniques, metal contamination ofthe underlying semiconductor substrates is not an issue, as is the casefor polymers based on norbornene (Chemical of Materials, 10 3319 (1998);10, 3328 (1998)). Furthermore, adamantane-containing temperature (T_(d))and good film-forming properties. Polymers based on higher diamondoidswould be expected to have even better properties.

Example 76 Soluble Higher Diamondoid-Containing Polyesters Based onDiamondoid Bisphenol

Polyarylates derived from bisphenol and iso/terephthalic acid are wellaccepted as highly thermally stable materials. However, polyarylates aregenerally difficult to process because of their limited solubility inorganic solvents and their high melting temperatures or high T_(g)'s byvirtue of their rigid structures. It has been reported thatincorporation of bulky pendant cardo groups, such as adamantly groups,into polymer backbones, results n enhanced thermal properties of thepolymers. compared with polymers containing aromatic bisphenols (FIG.37A). As an example of the type of polymer, FIG. 37B shows the design ofan iso-tetramantane containing polyester.

Example 77 Soluble Higher Diamondoid Containing Polyamides Based onDiamondoid Diamines

Aromatic polyamides attract much interest because of theirhigh-temperature resistance and mechanical strength. However, theapplications of polyamides are limited by processing difficultiesarising from their low solubility in organic solvents and their highglass transition or melting temperature. A number of successfulapproaches to increasing the solubility and processability ofpolyamides, without sacrificing their thermal stability, employ theintroduction of flexible or non-symmetrical linkages into the polymerbackbone or the incorporation of bulky substituents, such as pendantgroups, into the polymer backbone. The inter-chain interaction of thepolymers can be decreased by the introduction of bulky pendant groups,resulting in improved solubility of the polymers. Generally, theincorporation of pendant groups results in amorphous materials withincreased solubility in common organic solvents.

FIG. 38 presents an example of this design which incorporatesiso-tetramantane groups in the polyamide backbone.

Example 78 Soluble Diamondoid-Containing Polyimides Based on DiamondoidDiamines

The outstanding properties of aromatic polyimides, such as excellentthermo-oxidative stability and superior chemical resistance, led to theuse of polyimides in many applications such as insulating materials forelectronics, semipermeable membranes for gas separations, andhigh-temperature adhesives and coatings. (J. M. Sonnett, T. P. Gannett,Polyimides: Fundamental and Applications”, M. K. Ghosh and K. L. Mittal,Ed., Marcel Dekker, New York, 1996). However, in general, aromaticpolyimides are insoluble and intractable and are, only processable underextreme conditions. Therefore, a great deal of effort has focused onincreasing their processability while minimizing loss of their thermalstability. To overcome these processing problems, flexible or bulkygroups, such as adamantly groups, into the polymer backbone was shown toincrease both thermal stability and solubility in organic solvents, thusimproving the processability of polyimides. In addition, since such cagehydrocarbon groups are bulky, their incorporation into polymer backbonessignificantly improves the penetration of solvent molecules into thepolymer, thus increasing solubility. As an example, we now present apolyimide containing iso-tetramantane groups along its polymer backbone(FIG. 39A), and a design of polyaspartimide containing iso-tetramantylgroups (FIG. 40). It should be noted that the dianhydride could benon-aromatic or other aromatic dianhydrices as shown in FIG. 39B, forexample.

Example 79 Soluble Higher Diamondoid Containing Polyamide-imides Basedon Higher Diamondoid Diamide-Dicarboxylic Acids and Diamines

Aromatic polyimides are recognized as a class of high performancematerials because of their remarkable thermal and oxidative stabilitiesand their excellent electrical and mechanical properties, even duringlong periods of operation. Unfortunately, strong interactions betweenpolyimide chains and their rigid structure make them intractable. Poorthermoplastic fluidity and solubility are the major problems for wideapplications of polyimides. On the other hand, polyamides have theadvantage of good solubility and processability, as do polyetherimides.Therefore, polyamide-imide or polyetherimide might be the most usefulmaterials, combining the advantages of both polyimides (such ashigh-temperature stability) and polyamides (such as goodprocessability). In combination with the advantages of diamondoidhydrocarbons, we present a sample design of a polyamide-imide containingiso-tetramantyl groups in the polymer chain (FIG. 41). The diaminesinvolved in the polymerization reaction could be either higherdiamondoid diamides such shown in FIG. 40 or other aromatic diamines ortheir combinations. Selected examples of aromatic diamines are presentedin FIG. 42.

1. A higher diamondoid derivative containing a covalently-attachedmoiety replacing a hydrogen which is a polymerizable moiety or which canbe converted to a polymerizable moiety.
 2. The higher diamondoidderivative of claim 1 containing one or two polymerizable moieties. 3.The higher diamondoid derivative of claim 2 containing one polymerizablemoieties.
 4. The higher diamondoid derivative of claim 2 containing twopolymerizable moieties.
 5. The higher diamondoid derivative of claim 1having the formula:

wherein D is a higher diamondoid nucleus, and R¹, R², R³, R⁴, R⁵ and R⁶are independently selected from the group consisting of hydrogen and apolymerizable moiety; provided at least one of the R′s is apolymerizable moiety.
 6. The higher diamondoid derivative of claim 2wherein the polymerizable moieties are selected from alkenyl, alkynyl,OH, C₂H₃O, SH, NH₂, CO₂H, C₆H₅, C₆H₄NH₂, C₆H₄CO₂H or C₆H₄OH.
 7. Thehigher diamondoid derivative of claim 2, wherein the one or morepolymerizable moieties are attached to tertiary carbons of the higherdiamondoid.
 8. The higher diamondoid derivative of claim 5 wherein thehigher diamondoid is tetramantane.
 9. The higher diamondoid derivativeof claim 5 wherein the higher diamondoid is pentamantane.
 10. The higherdiamondoid derivative of claim 5 wherein the higher diamondoid ishexamantane.
 11. The higher diamondoid derivative of claim 5 wherein thehigher diamondoid is heptamantane.
 12. The higher diamondoid derivativeof claim 5 wherein the higher diamondoid is octamantane.
 13. The higherdiamondoid derivative of claim 5 wherein the higher diamondoid isnonamantane.
 14. The higher diamondoid derivative of claim 5 wherein thehigher diamondoid is decamantane.
 15. The higher diamondoid derivativeof claim 5 wherein the higher diamondoid is undecamantane.
 16. Thehigher diamondoid derivative of claim 5 wherein the polymerizable moietyhas the structure:—(X)_(m)—(Y)_(n)—Z wherein X is O, NR⁷, OC(O), NR⁸C(O), C(O)O orC(O)NR⁹, wherein R⁷, R⁸ and R⁹ are independently hydrogen or alkyl; Y isalkylene, arylene, alkarylene, heteroarylene or alkheteroarylene; Z isalkenyl, alkynyl, OH, C₂H₃O, SH, NH₂, CO₂H, C₆H₅, C₆H₄NH₂, C₆H₄CO₂H orC₆H₄OH m is 0 or 1; and, n is 0 or
 1. 17. The higher diamondoidderivative of claim 16, wherein there is one or two polymerizablemoieties on the derivative.
 18. The higher diamondoid derivative ofclaim 17, wherein there is one polymerizable moiety on the derivative.19. The higher diamondoid derivative of claim 17, wherein there are twopolymerizable moieties on the derivative.
 20. The higher diamondoidderivative of claim 16, wherein Z is selected from the group consistingof ethenyl, ethynyl, propenyl, propynyl, isobutenyl and butynyl.
 21. Thehigher diamondoid derivative of claim 16, wherein Z is selected from agroup consisting of OH and SH.
 22. The higher diamondoid derivative ofclaim 16, wherein Z is selected from a group consisting of NH₂, C₂H₃Oand CO₂H.
 23. The higher diamondoid derivative of claim 16, wherein Z isselected from a group consisting of C₆H₅, C₆H₄NH₂, C₆H₄CO₂H and C₆H₄OH.24. The higher diamondoid derivative of claim 16, wherein X is O, OC(O),NR⁷, NR⁸C(O), C(O)O, or C(O)NR⁹.
 25. The higher diamondoid derivative ofclaim 16, wherein m is 0 and Y is alkylene or arylene.
 26. The higherdiamondoid derivative of claim 16, wherein m is 0 and Y is alkylene. 27.The higher diamondoid derivative of claim 16, wherein m is 0 and n is 0.28. The higher diamondoid derivative of claim 24, wherein Y is —CH₂— or—(CH₂)₂—.
 29. A higher diamondoid intermediate containing acovalently-attached moiety replacing a hydrogen which is a polymerizablemoiety or which can be converted to a polymerizable moiety.
 30. Thehigher diamondoid intermediate of claim 29 containing one or twointermediate moieties.
 31. The higher diamondoid intermediate of claim30 containing one intermediate moieties.
 32. The higher diamondoidintermediate of claim 30 containing two intermediate moieties.
 33. Thehigher diamondoid intermediate of claim 29 having the formula:

wherein D is a higher diamondoid nucleus; and R¹⁰, R¹¹, R¹², R¹³, R¹⁴and R¹⁵ are independently selected from the group consisting of hydrogenand an intermediate moiety; provided at least one of the R′s is anintermediate moiety.
 34. The higher diamondoid intermediate of claim 33wherein the intermediate is present in an amount of at least 100 ppm ofthe composition in which it is present.
 35. The higher diamondoidintermediate of claim 34 wherein the intermediate moieties are selectedfrom H, F, Cl, Br, I, OH, SH, NH₂, NHCOCH₃, NHCHO, CO₂H, CO₂R′, COCl,CHO, CH₂OH, ═O, NO₂, —CH═CH₂, —C≡CH and C₆H₅; wherein R′ is alkyl. 36.The higher diamondoid intermediate of claim 34, wherein the one or moreintermediate moieties are attached to tertiary carbons of the higherdiamondoid.
 37. The higher diamondoid intermediate of claim 34 whereinthe higher diamondoid is tetramantane.
 38. The higher diamondoidintermediate of claim 34 wherein the higher diamondoid is pentamantane.39. The higher diamondoid intermediate of claim 34 wherein the higherdiamondoid is hexamantane.
 40. The higher diamondoid intermediate ofclaim 34 wherein the higher diamondoid is heptamantane.
 41. The higherdiamondoid intermediate of claim 34 wherein the higher diamondoid isoctamantane.
 42. The higher diamondoid intermediate of claim 34 whereinthe higher diamondoid is nonamantane.
 43. The higher diamondoidintermediate of claim 34 wherein the higher diamondoid is decamantane.44. The higher diamondoid intermediate of claim 34 wherein the higherdiamondoid is undecamantane.
 45. The higher diamondoid intermediate ofclaim 34 wherein R¹⁰ is an intermediate moiety with at most one other Rbeing an intermediate moiety.
 46. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is OH.
 47. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is Br.
 48. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is NH₂.
 49. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is CO₂H.
 50. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is ═O.
 51. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is F.
 52. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is Cl.
 53. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is I.
 54. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is NO₂.
 55. The higher diamondoid intermediate ofclaim 45, wherein R¹⁰ is CO₂CH₂CH₃.
 56. The higher diamondoidintermediate of claim 45, wherein R¹⁰ is COCl.
 57. The higher diamondoidintermediate of claim 45, wherein R¹⁰ is CHO.
 58. The higher diamondoidintermediate of claim 45, wherein R¹⁰ is CH.sub.2OH.
 59. The higherdiamondoid intermediate of claim 45, wherein R¹⁰ is CH═CH₂.
 60. Thehigher diamondoid intermediate of claim 45, wherein R¹⁰ is C≡CH.
 61. Thehigher diamondoid intermediate of claim 45, wherein R¹⁰ is C₆H₅.
 62. Thehigher diamondoid intermediate of claim 45, wherein R¹⁰ is SH.
 63. Thehigher diamondoid intermediate of claim 45, wherein R¹⁰ is NHCOCH₃. 64.The higher diamondoid intermediate of claim 45, wherein R¹⁰ is NHCHO.